CN104560169B - A kind of method for hydrogen cracking of producing heavy naphtha from high-nitrogen stock - Google Patents

A kind of method for hydrogen cracking of producing heavy naphtha from high-nitrogen stock Download PDF

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CN104560169B
CN104560169B CN201310523162.9A CN201310523162A CN104560169B CN 104560169 B CN104560169 B CN 104560169B CN 201310523162 A CN201310523162 A CN 201310523162A CN 104560169 B CN104560169 B CN 104560169B
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reaction
content
accordance
hydrogen
oil
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CN104560169A (en
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董建伟
赵广乐
张乐
蒋东红
赵阳
陈元君
毛以朝
胡志海
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Sinopec Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • 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
    • 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
    • C10G2300/1074—Vacuum distillates
    • 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)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

A kind of method for hydrogen cracking of producing heavy naphtha from high-nitrogen stock, after mixing with hydrogen-rich gas, high-nitrogen raw oil enters the first reaction zone through heating, there is hydrofining reaction and hydrocracking reaction, that reactant is flowed through is cooling, after Oil-gas Separation, obtain light naphthar, heavy naphtha and tail oil cut through fractionation, wherein tail oil cut is mixed into second reaction zone with recycle hydrogen and carries out hydrocracking reaction after supercharging. The tail oil cut that second reaction zone of the present invention can transform difficulty under high-speed, low severity condition is all converted into naphtha cut, the method that adopts the present invention to improve, reduce the lower product yields of added value such as dry gas, liquefied gas and light naphthar, improved the selective of heavy naphtha.

Description

A kind of method for hydrogen cracking of producing heavy naphtha from high-nitrogen stock
Technical field
The invention belongs to a kind of method for hydrogen cracking that obtains low boiler cut hydrocarbon ils in the situation that there is hydrogen. More specificallyGround is said, is a kind of method for hydrogen cracking of producing heavy naphtha.
Background technology
Since the second half year in 2009, global economy manifests recovery sign, and the demand of global petroleum chemicals is resumed the uptrend. In advanceThe global demand of meter from present to chemical products in 2015 increases by 60% will be from Asia, and the half of Asia demand growth during this time willFrom China. Benzene,toluene,xylene (being called for short BTX) is the basic material of petro chemical industry, is the important of high-knock rating gasolineComponent, the required BTX in the whole world has nearly 70% to be from catalytic reforming, and heavy naphtha is the primary raw material of catalytic reforming. WhenBefore, world's Petrochemical Enterprises faces a severe challenge: oil price Continued, and heavy inferior crude oil supply ratio increases; Petroleum chemicals needAsk unbalanced, part petroleum chemicals can not meet the demand of economic development, and feed naphtha is in short supply. How to utilize limited crude oilThe basic material of the acquisition petroleum chemicals of resource maximum, will become the outstanding problem that future, a period of time petrochemical industry faced.
Hydrocracking is one of main technique of heavy distillate deep processing, but prior art is mainly clean to produceFuel is main, carries out hydrocracking production and obtains the clean fuels such as high-quality jet fuel, diesel oil, for many by heavy distillateThe technology of producing heavy naphtha is relatively less. At present, the approach of voluminous heavy naphtha is mainly by improving reaction conversion ratio to increaseYield, although simple raising conversion level has improved heavy naphtha yield, light naphthar, liquefied gas, dry gas etc. are low value-addedProduct yield is corresponding increase also, and chemical hydrogen consumption also significantly rises, and economy is poor. It is anti-that the above heavy distillat of naphtha loops back crackingAnswer effectively heavy naphtha yield of device, and the aspect such as selective and chemical hydrogen consumption all has clear improvement at heavy naphtha. ButFor the higher cycloalkyl wax oil of character poor raw material, especially nitrogen content or wax tailings, still exist heavy naphtha yield low,Poor selectivity, high, the high deficiency of chemical hydrogen consumption of reaction severity. Therefore develop new hydrocracking technology by cycloalkyl decompression wattIt is to solve petroleum chemicals basic material that this oil, the contour nitrogen heavy charge of coker gas oil are converted into the aromatic hydrocarbons material such as naphtha as far as possibleOne of effective way of shortage.
The invention provides a kind of hydrogenation of processing the heavy inferior raw materials such as high nitrogen heavy vacuum gas oil, coker gas oil splitsChange method, adopts method provided by the present invention under the condition relaxing, the maximum of high selectivity, low hydrogen consumption to obtain heavyNaphtha.
CN101210195A discloses a kind of method for hydrogen cracking by poor heavy raw material more producing chemical industry light oil, the partyMethod adopts preferred Hydrobon catalyst and hydrocracking catalyst, once high by processing high-sulfur under flow process in single hop series connectionThe poor heavy raw material of nitrogen, naphtha yield can reach 35% left and right. The method adopts once passes through flow process, in the middle of the product part of holding concurrently, heats up in a steamerDivide oil and tail oil, naphtha yield is restricted.
CN101684415A discloses a kind of method for hydrogen cracking of producing chemical materials to maximum with low cost, the methodThe similar employing of flow process and the present invention Liang Ge hydrocracking reaction district. Hydrocracking section effluent, after separating, loops back secondary fissureChange reaction zone. The method has also been produced greatly when the raw materials such as decompressed wax oil are all transformed to the aromatic hydrocarbons raw materials for production such as naphthaThe tail oil of amount is as preparing ethylene by steam cracking device raw material.
Summary of the invention
The object of the invention is to provide on the basis of existing technology a kind of hydrogenation of producing heavy naphtha from high-nitrogen stockCracking method.
Method provided by the invention comprises:
(1) heavy distillate enters the first reaction zone through heating after mixing with hydrogen-rich gas, occur hydrofining reaction andAfter hydrocracking reaction, that reactant is flowed through is cooling, after Oil-gas Separation, gained hydrogen-rich gas is recycled to hydrogenation after compressor boostsRefining reaction device entrance and the second cracking reaction zone entrance, and use as cold hydrogen.
(2) step (1) gained liquid obtains light naphthar, heavy naphtha and tail oil cut, wherein tail oil cut warp through fractionationAfter supercharging, be mixed into the circulation of the second hydrocracking reaction district with recycle hydrogen;
(3) step (2) enters and separates and fractionating system with the reaction effluent of step (1).
(4) Hydrobon catalyst is the Hydrothermal Synthesis Hydrobon catalyst of high nitrogen removal performance newly developed.
Described heavy end oil density is generally at 0.91g/cm3Above, conventionally at 0.92g/cm3Above; Arene content oneAs more than 45%, conventionally more than 50%; Nitrogen content is generally more than 1500 μ g/g, conventionally more than 2000 μ g/g. Heavy heats up in a steamerDivide oil to comprise various hydrocarbon raw materials, typical raw material comprises cycloalkyl vacuum gas oil (VGO) (VGO), coker gas oil (CGO), de-dropOne or more the mixture such as blue or green oil (DAO).
Adopt the contour nitrogen weight of cycloalkyl vacuum gas oil (VGO), coker gas oil of method processing high nitrogen-containing provided by the inventionRaw material, can be at the reaction condition relaxing, and under relatively low chemical hydrogen consumption, the maximum of high selectivity is produced heavy naphtha.Gained naphtha cut can reach 88% heavy more than, wherein as produce aroamtic hydrocarbon raw material heavy naphtha fraction yield can reach 68% heavy withOn.
Described reaction condition is: hydrogen dividing potential drop 5.0～18.0MPa, 300～430 DEG C of reaction temperatures, cumulative volume 0.1～8.0h-1, hydrogen to oil volume ratio 300～3000Nm3/m3。
The present invention adopts two-stage method operating process, and wherein first paragraph is processed heavy distillate, and second segment is processed unconvertedTail oil cut, two sections of parallel operations, share high-low pressure separator and fractionating column and hydrogen gas system. First paragraph can adopt oneReactor, loads the combination catalyst of Hydrobon catalyst and hydrocracking catalyst in reactor; First paragraph can also be adoptedWith two reactor serial flows, the first reactor charge Hydrobon catalyst, the second reactor charge hydrocracking catalysisAgent. Second segment adopts a reactor, filling hydrocracking catalyst.
In hydrocracking process, the activity of cracking reaction derives from acidic zeolite center, and organic nitrogenize in raw materialThing is easily adsorbed on acid centre, causes cracking activity to reduce, even loss of activity. Therefore, alive for ensureing Cracking catalystThe stability of property, need make hydrofining reactor export oily nitrogen content lower than certain control index. Hydrobon catalystDenitrification activity higher, hydrofining reaction condition just more relaxes. In other words, adopt the hydrofinishing catalysis of high denitrification activityAgent, can reduce the average reaction temperature of hydrofining reactor or the consumption of minimizing Hydrobon catalyst.
The Hydrobon catalyst that the present invention adopts hydro-thermal treatment preparation method thereof to obtain. This Hydrobon catalyst has by forceNitrogen removal performance, its preparation method is as follows:
With a kind of porous carrier of aqueous solution dip forming, the mixture that dipping is obtained carries out water in closed reactorHeat treatment, and the solid product that hydrothermal treatment consists is obtained is dried, described porous carrier contains heat-resistant inorganic oxide and largePorous molecular sieve, the described aqueous solution contains at least one containing the compound of group VIII metal and at least one is containing group vib metalCompound and containing or containing cosolvent.
Said method comprises the porous carrier that carrys out dip forming with a kind of aqueous solution, and the described aqueous solution contains at least oneCompound containing group vib metal contains the compound of group VIII metal and contains or do not contain cosolvent with at least one.
In the described aqueous solution, the described concentration that contains the compound of group vib metal and contain the compound of group VIII metal,Can meet concrete use with the content of group vib metal and group VIII metal in the catalyst that can make finally to prepare wantsAsk and be as the criterion. Usually, in the time that prepared according to the methods of the invention catalyst is used for the hydrocracking of hydrocarbon ils, in the described aqueous solutionContaining the total amount of the compound of group vib metal and make the catalyst of preparation containing the total amount of the compound of group VIII metalIn, in oxide, the content of group vib metal is 10-50 % by weight, is preferably 10-45 % by weight; Containing of group VIII metalAmount, for 1-10 % by weight, is preferably 1-7 % by weight; The content of porous carrier is 40-89 % by weight, is preferably 48-89 % by weight.
Described group vib metal and described group VIII metal can be that the routine of this area is selected. According to the present inventionThe catalyst prepared of method during for the hydrocracking of hydrocarbon ils, described group vib metal is preferably molybdenum and/or tungsten, describedVIII family metal is preferably cobalt and/or nickel.
Can pass through the compound that contains group vib metal conventional this area and molten containing the compound of group VIII metalIn Xie Shui, thereby prepare the described aqueous solution.
The described compound that contains group vib metal can be the conventional water-soluble chemical combination containing group vib metal in this areaThing, the described compound containing group VIII metal can be the conventional water soluble compound containing group VIII metal in this area.
Particularly, the described compound that contains group vib metal can be ammonium molybdate, ammonium paramolybdate, ammonium metatungstate, molybdenum oxideWith one or more in tungsten oxide.
The described compound containing group VIII metal can be the nitrate of group VIII metal, the chlorine of group VIII metalThe sulfate of compound, group VIII metal, the formates of group VIII metal, the acetate of group VIII metal, group VIIIThe oxalates of the phosphate of metal, the citrate of group VIII metal, group VIII, the carbonate of group VIII metal,The subcarbonate of VIII family metal, the hydroxide of group VIII metal, the phosphate of group VIII metal, group VIII goldThe molybdate of the sulfide of phosphide, the group VIII metal belonging to, the aluminate of group VIII metal, group VIII metal, theOne or more in the tungstates of VIII family metal and the water-soluble oxide of group VIII metal; Be preferably group VIII goldThe acetate of the nitrate of oxalates, the group VIII metal belonging to, the sulfate of group VIII metal, group VIII metal, theThe chloride of VIII family metal, the carbonate of group VIII metal, the subcarbonate of group VIII metal, group VIII metalHydroxide, the phosphate of group VIII metal, the molybdate of group VIII metal, the tungstates and of group VIII metalOne or more in the water-soluble oxide of VIII family metal.
Particularly, the described compound containing group VIII metal can for but be not limited to: nickel nitrate, nickelous sulfate, nickel acetate,One or more in basic nickel carbonate, cobalt nitrate, cobaltous sulfate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and nickel chloride.
The described aqueous solution can also contain the conventional various cosolvents in this area, described containing group vib metal to improveCompound and the dissolubility of the described compound containing group VIII metal in water; Or stablize the described aqueous solution, preventPrecipitation. Described cosolvent can, for the conventional various materials that can realize above-mentioned functions in this area, be not particularly limited. ExampleAs, described cosolvent can be one or more in phosphoric acid, citric acid and ammoniacal liquor. The present invention does not have for the concentration of described ammoniacal liquorBeing particularly limited, can be that the routine of this area is selected, and is not particularly limited. The consumption of described cosolvent can be this areaConventional selection, usually, in the described aqueous solution, the content of described cosolvent can be 1-10 % by weight.
The method according to this invention, described porous carrier contains heat-resistant inorganic oxide and large pore molecular sieve. In the present invention,In described porous carrier, what the content of described heat-resistant inorganic oxide and large pore molecular sieve can be according to the catalyst of final preparationSuitable selection is carried out in application scenario. In the time that prepared according to the methods of the invention catalyst is used for the hydrocracking of hydrocarbon ils, withThe total amount of described porous carrier is benchmark, and the content of described large pore molecular sieve can be 2-75 % by weight, is preferably 5-60 % by weight,More preferably 5-40 % by weight, more preferably 5-30 % by weight; The content of described heat-resistant inorganic oxide can be heavy for 25-98Amount %, is preferably 40-95 % by weight, more preferably 60-95 % by weight, more preferably 70-95 % by weight.
According to the present invention, described heat-resistant inorganic oxide can be the conventional various heat-resistant inorganic oxides in this area. OneAs, described heat-resistant inorganic oxide can be aluminium oxide, silica, titanium oxide, magnesia, aluminium oxide-silicon oxide, oxidationSilicon-magnesia, silica-zirconia, silica-thorium oxide, silica-beryllium oxide, silica-titanium oxide, silica-oxidationZirconium, oxidation titania-zirconia, silica-alumina-thorium oxide, silica-alumina-titanium oxide, silica-alumina-oxidationOne or more in magnesium and silica-alumina-zirconia.
Preferably, described heat-resistant inorganic oxide is aluminium oxide. Described aluminium oxide can be the conventional various oxygen in this areaChange aluminium. Usually, described aluminium oxide can be in gama-alumina, η-aluminium oxide, θ-aluminium oxide, δ-aluminium oxide and χ-aluminium oxideOne or more. According to the present invention, described aluminium oxide can also contain and is selected from one in titanium, magnesium, boron, zirconium, thorium, niobium and rare earthPlant or multiple interpolation component. In the present invention, the content of described interpolation component can carry out suitably according to concrete application scenarioSelection, preferably, at prepared according to the methods of the invention catalyst during for the hydrocracking of hydrocarbon ils, described aluminium oxideIn, the total amount of described interpolation component is 1-30 % by weight. According to the present invention, described aluminium oxide is preferably gama-alumina, or containsThere is one or more the gama-alumina of interpolation component being selected from titanium, magnesium, boron, zirconium, thorium, niobium and rare earth.
In the present invention, described large pore molecular sieve refers to the zeolite molecular sieve with twelve-ring pore structure. For example, described largePorous molecular sieve can for have faujasite structure zeolite molecular sieve, there is the zeolite structured zeolite molecular sieve of Beta and haveOne or more in the zeolite molecular sieve of mordenite structure.
Preferably, described large pore molecular sieve is y-type zeolite.
More preferably, described large pore molecular sieve is HY zeolite, rare-earth type Y zeolite (, REY zeolite), rare-earth type HY zeolite(, REHY zeolite), overstable gamma zeolite (, USY zeolite), rare-earth type overstable gamma zeolite (, REUSY zeolite), phosphorous Y type boilOne or more in stone, phosphorous overstable gamma zeolite, phosphorous HY type zeolite and dealuminium Y type beta stone.
Further preferably, described large pore molecular sieve has B acid and L acid, and described B acid is large with the mol ratio of described L acidIn 0.9, and described zeolite molecular sieve is at 3685-3760cm-1There is at least one characteristic peak corresponding to silicon hydroxyl.
Still more preferably, described B acid is 1-10 with the mol ratio of described L acid, and described large pore molecular sieve is at 3685-3760cm-1There are two characteristic peaks corresponding to silicon hydroxyl.
The method according to this invention, what described porous carrier can also contain effective dose can further improve final preparationThe auxiliary agent of performance of catalyst, as P elements. Can adopt the conventional the whole bag of tricks in this area to draw in described porous carrierEnter described auxiliary agent, repeat no more herein.
According to the present invention, when the method for extruding in employing is carried out moulding, described mixture can also contain extrusion aid and/or glueStick. The kind of described extrusion aid, peptizing agent and consumption are conventionally known to one of skill in the art, do not repeat them here.
According to the present invention, the formed body of extruding is carried out to the condition of roasting and can select for the routine of this area. For example, instituteThe temperature of stating roasting can be 350-650 DEG C, is preferably 400-600 DEG C; The time of described roasting can be 2-6 hour, preferablyFor 3-5 hour.
The method according to this invention also comprises that the mixture that dipping is obtained carries out hydrothermal treatment consists, and described hydrothermal treatment consists is being pressedPower is to carry out under the condition of P0+ Δ P.
In the present invention, P0 is described porous carrier, described compound, the described group vib gold that contains containing group VIII metalThe pressure that water in the compound belonging to, cosolvent and the described aqueous solution that contains or do not contain produces in hydrothermal treatment consists.
The method according to this invention, in described hydrothermal treatment consists process, for carrying out the pressure in the closed container of hydrothermal treatment consistsPower except described porous carrier, described compound containing group VIII metal, described contain the compound of group vib metal, containing or notOutside the pressure of the water generates in the cosolvent containing and the described aqueous solution, also comprising Δ P, is 0.05-15MPa. Preferably, Δ PFor 0.1-10MPa. From the catalytic activity of catalyst and the angle of the internal pressure that described closed container bears of the final preparation of balanceDegree sets out, more preferably 0.2-8MPa of Δ P.
In the present invention, pressure is all in gauge pressure.
Can adopt the conventional the whole bag of tricks in this area to make described hydrothermal treatment consists is to enter under the condition of P0+ Δ P at pressureOK.
In the present invention, making described hydrothermal treatment consists is that the mode of carrying out under the condition of P0+ Δ P comprises at pressure: in volatilizationUnder the existence of organic matter and non-active gas, carry out described hydrothermal treatment consists, described volatile organic matter and non-active gas totalIt is Δ P that addition makes the gross pressure that described volatile organic matter and non-active gas produce in hydrothermal treatment consists.
Can adopt variety of way that described hydrothermal treatment consists is carried out under the existence of described volatile organic matter. For example,Can add described volatile organic matter to the aqueous solution for flooding described porous carrier, thereby make described hydro-thermal placeReason is carried out under the existence of volatile organic matter; Also can be by described in carrying out passing in the closed container of described hydrothermal treatment consistsVolatile organic matter, thus described hydrothermal treatment consists is carried out under the existence of volatile organic matter. From further raising preparationThe angle of catalytic activity of catalyst set out, the method according to this invention is preferably to the closed container that carries out described hydrothermal treatment consistsIn pass into volatile organic matter, thereby described hydrothermal treatment consists is carried out under the existence of volatile organic matter.
In the present invention, described volatile organic matter can be transformed into by liquid state for various under hydrothermal treatment consists conditionThe material of gaseous state and/or can decompose the material of the gas of generation under hydrothermal treatment consists condition. For example, described volatile organic matterCan be for being selected from one or more organic matters in the polyethylene glycol that alcohol, acid, amine and number-average molecular weight are 200-1500. PreferablyGround, described volatile organic matter is fatty alcohol, the aliphatic acid of C2-C30, the fatty amine of C2-C30, the C6-C30 that is selected from C1-C30Alkane and the number-average molecular weight polyethylene glycol that is 200-1500 in one or more. More preferably, described volatility is organicThing is the fatty alcohol that is selected from C1-C12, the aliphatic acid of C2-C10, the fatty amine of C2-C12, alkane and the number-average molecular weight of C6-C12For one or more in the polyethylene glycol of 200-1500. Further preferably, described volatile organic matter is selected from the fat of C1-C8One or more in the alkane of the aliphatic acid of fat alcohol, C2-C5, the fatty amine of C2-C7 and C6-C11.
Particularly, described volatile organic matter can for be selected from normal propyl alcohol, isopropyl alcohol, ethylene glycol, glycerine, triethylene glycol,Number-average molecular weight is polyethylene glycol, diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, the aminotriacetic acid, 1 of 200-1500,2-CDTA, tartaric acid, malic acid, ethylenediamine, hexane and isomers thereof, heptane and isomers thereof, octane andOne or more in its isomers and decane and isomers thereof.
In the present invention, described non-active gas refers to can be with porous carrier, containing group vib gold in hydrothermal treatment consists processThe compound that belongs to, containing compound, cosolvent and the water of group VIII metal, chemically interactive gas occurring, can be abilityThe various non-active gas that territory is conventional. Preferably, described non-active gas (for example: argon is selected from nitrogen, group 0 element gasGas), the hydrocarbon of carbon dioxide, sulfur hexafluoride and C1-C5.
The method according to this invention, the time of described hydrothermal treatment consists and temperature can be that the routine of this area is selected, as long asThe pressure of described hydrothermal treatment consists meets previously described requirement. Preferably, the temperature of described hydrothermal treatment consists can be 100-200 DEG C; The time of described hydrothermal treatment consists can be 0.5-36 hour, is preferably 1-24 hour.
The method according to this invention is dried after also comprising the mixture filtration that hydrothermal treatment consists is obtained. The present invention forDescribed dry condition is not particularly limited, and can be that the routine of this area is selected. Usually, described dry condition comprises:Temperature can be 100-300 DEG C, is preferably 100-280 DEG C, more preferably 100-250 DEG C; Time can be 1-12 hour, preferablyFor 2-8 hour.
The method according to this invention can also comprise carries out roasting by the dry solid matter obtaining. The condition of described roastingThe routine that can be this area is selected. Usually, the condition of described roasting comprises: temperature can be 350-550 DEG C, is preferably400-500 DEG C; Time can be 1-8 hour, is preferably 2-6 hour.
The composition of preferred Hydrobon catalyst: taking catalyst as benchmark, the heavy % of nickel oxide 1～10, molybdenum oxide and oxidationTungsten sum is 10～50 heavy %, the heavy % of fluorine 1～10, and the heavy % of phosphorus pentoxide 0.5～8, surplus is silica-alumina; Taking carrier asBenchmark, silica content is 2～45 heavy %, alumina content is 55～98 heavy %.
Preferred Hydrobon catalyst, denitrification activity is active higher by 30% than the hydrodenitrogenation catalyst of current advanced levelLeft and right, or reaction temperature can reduce by 8～10 DEG C while reaching identical denitrification percent, and aromatic saturation performance is also refining higher than advanced levelCatalyst. The hydrogenation saturated reaction of aromatic hydrocarbons be its open loop cracking must be through step, the present invention adopt Hydrobon catalyst toolHave good aromatic saturation performance, especially the hydrogenation of polycyclic aromatic hydrocarbon is saturated can to promote aromatic hydrocarbons in feedstock oil, for cracking zone providesBe easy to occur the charging of cracking reaction, improve feedstock oil conversion ratio.
Hydrocracking catalyst of the present invention is that one is become carrier loaded at least one with alumina composite by zeoliteKind of group VIII and the metal component of at least one group vib and the catalyst of organic additive, VIII family metal be selected from Co or/And Ni, group vib metal is selected from Mo or/and W, described organic additive be selected from containing a kind of in oxygen or nitrogenous organic compound orSeveral.
The composition of preferred hydrocracking catalyst is by weight: alumina content is 15～65%, and preferably 35～55%;Zeolite content is 20～75%, preferably 45～65%; Organic additive 1～10%; Nickel oxide content is 0.5～15%, preferably2.0～3.4%; Tungsten oxide content is 10～45%, preferably 20～34%.
Described zeolite is selected from one or more in faujasite, Beta zeolite, y-type zeolite and modenite.
Preferred oxygen-containing organic compound is selected from one or more in Organic Alcohol, organic acid; Preferred nitrogenous organisingCompound is selected from one or more in organic amine, organic ammonium salt. For example, oxygenatedchemicals can be ethylene glycol triol, poly-secondGlycol (molecular weight is 200～2000), diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, citric acid, wineOne or more in stone acid; Itrogenous organic substance can be ethylenediamine, ethylenediamine tetra-acetic acid and ammonium salt thereof.
The preparation method of this hydrocracking catalyst is as follows: the predecessor of zeolite, aluminium oxide and/or aluminium oxide or what thing are pressedMix according to the desired ratio of catalyst, roll rear extrusion, after drying roasting, make carrier. By what prepare according to a certain percentageActive metal salting liquid is mixed with mixed solution with preferred organic matter, and carrier is joined in solution and floods certain hour, filtersRemove surplus solution, then dry, activation obtains finished catalyst.
Preferred hydrocracking catalyst selectivity of ring-opening is good, has the feature of high activity, high heavy naphtha yield. With work asFront high-caliber hydrocracking agent is compared, and in the situation that conversion ratio is certain, can obtain the heavy naphtha fraction of higher yield. ThisOutward, the high cracking activity feature of preferred hydrocracking catalyst, can more operate under high-speed, urges than conventional hydrocrackingAgent company improves more than 20%, and catalyst heap is than reducing by 15～30%, has both saved the loadings minimizing reactor of catalystVolume, has reduced again the Unit Weight cost of catalyst, thereby reduces investment.
For ensureing the long-term operation of commercial plant, on Hydrobon catalyst, load protective agent, protective agent is loadGroup vib metal in amorphous alumina or silica-alumina supports or VIII family non-precious metal catalyst or their combination. This type ofProtective agent has larger pore volume and specific area. The volume ratio of protective agent and Hydrobon catalyst is 0:100～20:100,Preferably 5:100～15:100.
For preventing H2S further reacts generation mercaptan sulfur with the issuable alkene of cracking process, at hydrocracking reactionA certain amount of Hydrobon catalyst of device bottom filling, after this volume ratio of catalyst for refining and Cracking catalyst be 5:100～20:100, preferably 10:100～15:100. The light-end products of gained of the present invention comprise light naphthar and heavy naphtha fraction. PumiceCerebrol cut can be used as gasoline blend component, also can be used as preparing ethylene by steam cracking raw material; Heavy naphtha fraction is rich in aromatic hydrocarbons, canDirectly as raw materials for catalytic reforming device.
Distinguishing feature of the present invention is to adopt the concept of reaction subregion for the treatment of high nitrogen heavy charge, raising heavy naphthaSelective.
, can under the condition comparatively relaxing, make by adopting described high-performance Hydrobon catalyst at the first reaction zoneHigh nitrogen heavy charge reaches the target of denitrogenation, aromatic saturation, and the first reaction zone arranges partial cracking transformation function simultaneously, by raw materialIn oil, easily transform portion is converted into heavy naphtha and light components more, and this portioned product goes out device after separating, to avoid theTwo reaction zone generation secondary crackings, make heavy naphtha be converted into more light components. This reaction zone heavy naphtha yield is controlled at 15%～45%, reaction condition relaxes, heavy naphtha yield and selectively higher. The first reaction zone effluent is through through separating, after fractionationThe cracking that circulates in second reaction zone of all the other difficult transform portion.
Second reaction zone is hydrocracking reaction district, and in this reaction zone reaction system, ammonia content is close to zero, without ammonia reactEnvironment is conducive to the performance of hydrocracking catalyst activity. Therefore, the second cracking reaction zone can be realized at high-speed, low severityUnder condition, difficult transform portion more than naphtha cut is all converted into naphtha cut. Lower reaction severity meansCracking zone reaction temperature is lower, and heat cracking reaction degree is also effectively controlled at lower temperature, dry gas, liquefied gas withAnd the lower product yield of added value such as light naphthar reduces to some extent, there is higher heavy naphtha selective. Two reaction zonesThe hydrocracking catalyst loading can be the same or different, hydrocracking catalyst type and the reaction in differential responses districtCondition is according to dissimilar raw material flexible operating, to ensure the production heavy naphtha of maximum under the condition relatively relaxing,And reduce gas and pumice productive rate, make reaction reach optimum.
In addition the two-stage reaction adopting in the present invention, shares piece-rate system and hydrogen gas system can be simplified process flow greatlyJourney, reduces cost of equipment and energy consumption. Common recycle hydrogen can also reduce hydrocracking catalyst in second reaction zone and lose sulphur phenomenon,Guarantee catalyst activity is stable.
Brief description of the drawings
Accompanying drawing is a kind of method for hydrogen cracking flow process signal of producing heavy naphtha from high-nitrogen stock provided by the present inventionFigure.
Detailed description of the invention
Below in conjunction with accompanying drawing, method provided by the present invention is further detailed.
Accompanying drawing is that the flow process of a kind of method for hydrogen cracking from high-nitrogen stock production heavy naphtha provided by the present invention is shownIntention. Some auxiliary equipment in figure do not mark as heat exchanger etc., but this is known to those of ordinary skill in the art.
A kind of method for hydrogen cracking flow process from high-nitrogen stock production heavy naphtha provided by the present invention is as follows:
Feedstock oil through pipeline 1 with mix from the recycle hydrogen of pipeline 23, then enter the first reactor 2, feedstock oil and hydrogenThere is desulfurization, denitrogenation and aromatic saturation reaction in gas, after reaction, logistics is directly entered through pipeline 3 under Hydrobon catalyst effectEnter the second reactor 4, oil, gas continue to react under hydrocracking catalyst effect. The generation logistics of the second reactor is complied withInferiorly enter high-pressure separator 6 through pipeline 5,19 and carry out Oil-gas Separation, for preventing that ammonium salt crystallization from separating out blocking pipeline, in the second reactionDevice 4 exports through pipeline 18 water filling washings. High-pressure separator 6 top gas enter circulating hydrogen compressor 21, hydrogen rich gas through pipeline 20After body supercharging, mixes with the new hydrogen supplementing through pipeline 22, return to the first reactor 2 and the 3rd reactor 16 through pipeline 23 and circulate and makeWith. The isolated liquid of high-pressure separator 6 enters low pressure separator 8 through pipeline 7 and carries out further Oil-gas Separation, and low pressure separatesThe isolated gas of device 8 is through pipeline 9 emptying, and isolated liquid enters fractionating column 11 through pipeline 10, the isolated lighter hydrocarbons of tower top,Light naphtha fraction is through pipeline 12 ejectors, and top side line is extracted heavy naphtha fraction out through pipeline 13. More than heavy naphthaTail oil cut can be extracted fractionating column out through pipeline 14, also can supercharging after through pipeline 15 be mixed into the from the recycle hydrogen of pipeline 23Three reactors 16, oil, gas carry out secondary response under the effect of hydrocracking catalyst, and the product of the 3rd reactor 16 is flowed throughPipeline 17 enters piece-rate system through pipeline 19 after mixing with from the generation logistics of the second reactor 4.
The following examples will be further described this method, but therefore not limit this method.
In embodiment, the business trade mark of the hydrocracking catalyst that uses is RHC-5, and in comparative example, hydrofinishing used is urgedThe business trade mark of agent is RN-32V, is Sinopec catalyst branch company Chang Ling catalyst plant and produces. Used in embodimentHydrobon catalyst is to adopt the high nitrogen removal performance catalyst A that in the present invention prepared by following hydro-thermal treatment preparation method thereof.
Its concrete preparation process is: by 300 grams of phosphorous y-type zeolites (Chang Ling catalyst plant produce, commodity are called PSRY,Lattice constant isPhosphorus content is 5 % by weight), (Shandong Aluminum Plant produces, trade name SD for 700 grams of butt boehmitesPowder, contents on dry basis is 69 % by weight) and 30 grams of sesbania powder mix, being extruded into circumscribed circle diameter with extruder is the trilobal of 1.6 millimetersBar. The formed body of extruding is dried to 5 hours at 120 DEG C, then 550 DEG C of roastings 3 hours, makes carrier S 3. In carrier S 3, largeThe content of porous molecular sieve is 30 % by weight, and the content of aluminium oxide is 70 % by weight.
20 grams of basic nickel carbonates are joined in 150 ml waters, follow to stir to add 8 grams of phosphoric acid heating stirring and dissolving, companionAdd respectively 12 grams of ammonium molybdates and 110 grams of ammonium metatungstates with stirring, after dissolving, add water and be settled to 200 milliliters. Adopt excessive dipping100 grams of carrier S 3 of above-mentioned aqueous solution dipping for method, dip time is 0.5 hour. The mixture that dipping is obtained is placed in heightPress in reactor, and add 15 milliliters of isopropyl alcohols, carry out hydrothermal treatment consists, the condition of hydrothermal treatment consists comprises: temperature is 100 DEG C, timeBetween be 24 hours, in hydrothermal treatment consists process, to passing into argon gas in autoclave, to make the pressure in autoclave be 3.3MPa,Wherein, P0=0.3MPa, Δ P=3.0MPa. The mixture that hydrothermal treatment consists is obtained is cooled to room temperature, after filtration, by what obtainSolid 120 DEG C dry 2 hours, then 200 DEG C dry 3 hours again, obtain catalyst A, the consisting of of catalyst A, to urgeAgent entirety is benchmark, and in oxide, tungsten is 30.4 % by weight, and molybdenum is 3.1 % by weight, and nickel is 4.2 % by weight.
Comparative example 1
Taking the high nitrogen heavy of one VGO as feedstock oil A, its feedstock property is as table 1. Adopt catalyst provided by the invention, formerAfter material oil enters high-pressure separator after refining reaction device, cracker, go out product, the above cut of heavy naphtha is without circulation. RealTest and the results are shown in table 2-table 4.
Comparative example 2
Taking the mixed material oil B containing VGO and CGO as raw material, adopt two sections of conventional boiling ranges, the first reaction zone only loads and addsHydrogen catalyst for refining, hydrocracking catalyst is only loaded in second reaction zone, and product is after separating, and the above cut of heavy naphtha circulatesGo back to second reaction zone and realize full conversion. Experimental result is listed in table 5-table 7.
Embodiment 1
The present embodiment adopts the feedstock oil identical with comparative example 1, with Hydrobon catalyst A provided by the present invention and workProcess flow carries out hydrocracking test, and experimental result is listed in table 2-table 4.
As can be seen from the table, producing in the heavy naphtha situation of same amount, adopt side provided by the present inventionMethod is with once by compared with flow process, and required hydrogen consumes still less, and heavy naphtha virtue is dived higher.
Embodiment 2
The present embodiment adopts the mixed material oil B containing VGO and CGO, with catalyst provided by the present invention and technological processCarry out hydrocracking test, experimental result is listed in table 5-table 7.
As can be seen from the table, adopt the method provided by the present invention can be by under the condition of hydrogen dividing potential drop 13.0MPaThe yield of tail oil is down to minimum, is 0; And maximum production obtains light naphthar and heavy naphtha product, total recovery reaches 89 heavy %Above. Show this method can be under the condition relatively relaxing the production naphtha of maximum.
Table 1, feedstock oil character
Feedstock oil title A B
Density, g/cm3 0.921 0.930 8 -->
S, heavy % 2.5 2.7
N，μg/g 1800 2400
Boiling range (D-1160), DEG C
Initial boiling point 323 318
50% 456 454
90% 523 528
95% 545 539
BMCI value 47.1 51.2
Table 2, comparative example 1 and embodiment 1 reaction condition
Table 3, comparative example 1 and embodiment 1 product distributed data
Comparative example 1 Embodiment 1
Chemical hydrogen consumption, heavy % 2.30 2.23
Product distributes, heavy %
H2S 2.66 2.66 9 -->
NH3 0.22 0.22
C1+C2 0.29 0.28
C3+C4 3.42 3.07
C5-light naphthar 7.53 7.42
Heavy naphtha 34.49 35.05
Boat coal 13.60 11.79
Diesel oil 14.32 13.48
Tail oil 25.77 28.28
Table 4, comparative example 1 and embodiment 1 product main character
Table 5, comparative example 2 and embodiment 2 reaction conditions
Table 6, comparative example 2 and embodiment 2 product distributed datas
Project Comparative example 2 Embodiment 2
Chemical hydrogen consumption, heavy % 3.37 3.30
Product distributes, heavy %
H2S 2.87 2.87
NH3 0.29 0.29
C1+C2 0.80 0.76
C3+C4 11.39 10.52
C5-light naphthar 21.63 20.24
Heavy naphtha 66.39 68.62
Table 7, embodiment 2 product main character

Claims (15)

1. a method for hydrogen cracking of producing heavy naphtha from high-nitrogen stock, comprising:
(1) heavy distillate enters the first reaction zone through heating after mixing with hydrogen-rich gas, and hydrofining reaction and hydrogenation occurAfter cracking reaction, that reactant is flowed through is cooling, after Oil-gas Separation, gained hydrogen-rich gas is recycled to hydrofinishing after compressor boostsReactor inlet and second reaction zone entrance, and use as cold hydrogen;
(2) step (1) gained liquid obtains light naphthar, heavy naphtha and tail oil cut through fractionation, and wherein tail oil cut is through superchargingBe mixed into second reaction zone with recycle hydrogen afterwards and carry out hydrocracking reaction;
(3) step (2) enters same piece-rate system and fractionating system with the reaction effluent of step (1);
The first reaction zone and second reaction zone are paralleling model operation;
In the first reaction zone, adopt a reactor, in reactor, load successively Hydrobon catalyst and hydrocracking catalysisAgent; Or, in the first reaction zone, adopt two reactor serial flows, the first reactor charge Hydrobon catalyst, secondReactor charge hydrocracking catalyst; Described Hydrobon catalyst is the hydrofinishing that hydro-thermal treatment preparation method thereof obtainsCatalyst, with a kind of porous carrier of aqueous solution dip forming, the mixture that dipping is obtained carries out water in closed reactorHeat treatment, and the solid product that hydrothermal treatment consists is obtained is dried, described porous carrier contains heat-resistant inorganic oxide and largePorous molecular sieve, the described aqueous solution contains at least one containing the compound of group VIII metal and at least one is containing group vib metalCompound and containing or containing cosolvent; Described hydrothermal treatment consists is to carry out under the condition of P0+ Δ P at pressure, and P0 is described manyHole carrier, described compound containing group VIII metal, described contain the compound of group vib metal, containing or the cosolvent that do not contain,And the pressure that produces in hydrothermal treatment consists of water in the described aqueous solution, Δ P is 0.05-15MPa.
2. in accordance with the method for claim 1, it is characterized in that, described heavy end oil density is at least 0.91g/cm3WithUpper, arene content is greater than more than 45%, and nitrogen content is greater than 1500 μ g/g.
3. in accordance with the method for claim 1, it is characterized in that, described heavy end oil density is at least 0.92g/cm3WithUpper, arene content is greater than more than 50%, and nitrogen content is greater than 2000 μ g/g.
4. according to the method described in claim 2 or 3, it is characterized in that, heavy distillate is selected from cycloalkyl vacuum gas oil (VGO), JiaoChange one or more in gas oil, deasphalted oil.
5. in accordance with the method for claim 1, it is characterized in that, reaction condition is: hydrogen dividing potential drop 5.0～18.0MPa, reaction temperatureSpend 300～430 DEG C, cumulative volume 0.1～8.0h-1, hydrogen to oil volume ratio 300～3000Nm3/m3。
6. in accordance with the method for claim 1, it is characterized in that, containing the compound of group vib metal in the described aqueous solutionTotal amount and making containing the total amount of the compound of group VIII metal in the catalyst of preparation, in oxide, group vib metalContent be 10-50 % by weight, the content of group VIII metal is 1-10 % by weight, the content of porous carrier is that 40-89 is heavyAmount %.
7. in accordance with the method for claim 6, it is characterized in that, containing the compound of group vib metal in the described aqueous solutionTotal amount and making containing the total amount of the compound of group VIII metal in the catalyst of preparation, in oxide, group vib metalContent for for 10-45 % by weight; The content of group VIII metal is 1-7 % by weight; The content of porous carrier is that 48-89 is heavyAmount %.
8. in accordance with the method for claim 1, it is characterized in that, described group vib metal is preferably molybdenum and/or tungsten, described inGroup VIII metal is preferably cobalt and/or nickel.
9. in accordance with the method for claim 8, it is characterized in that, the described compound that contains group vib metal be selected from ammonium molybdate,One or more in ammonium paramolybdate, ammonium metatungstate, molybdenum oxide and tungsten oxide.
10. in accordance with the method for claim 8, it is characterized in that, the described compound containing group VIII metal is selected from nitric acidIn nickel, nickelous sulfate, nickel acetate, basic nickel carbonate, cobalt nitrate, cobaltous sulfate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and nickel chlorideOne or more.
11. in accordance with the method for claim 1, it is characterized in that, described cosolvent is selected from phosphoric acid, citric acid and ammoniacal liquorOne or more, in the described aqueous solution, the content of described cosolvent is 1-10 % by weight.
12. in accordance with the method for claim 1, it is characterized in that, described porous carrier contains heat-resistant inorganic oxide and largePorous molecular sieve, taking the total amount of described porous carrier as benchmark, the content of described large pore molecular sieve is 2-75 % by weight, described heat-resistingThe content of inorganic oxide is 25-98 % by weight.
13. in accordance with the method for claim 1, it is characterized in that, described porous carrier contains heat-resistant inorganic oxide and largePorous molecular sieve, taking the total amount of described porous carrier as benchmark, the content of described large pore molecular sieve is 5-40 % by weight; Described heat-resistingThe content of inorganic oxide is 60-95 % by weight.
14. in accordance with the method for claim 1, it is characterized in that, heat-resistant inorganic oxide refers at oxygen or oxygen-containing atmosphereUnder, decomposition temperature is not less than the inorganic oxygen-containing compound of 300 DEG C.
15. in accordance with the method for claim 1, it is characterized in that, described large pore molecular sieve refers to have twelve-ring hole knotThe zeolite molecular sieve of structure.
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Patentee after: CHINA PETROLEUM & CHEMICAL Corp.

Patentee after: Sinopec Petrochemical Research Institute Co.,Ltd.

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