CN104560169A - Hydrocracking method for producing heavy naphtha from high-nitrogen stock - Google Patents
Hydrocracking method for producing heavy naphtha from high-nitrogen stock Download PDFInfo
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- CN104560169A CN104560169A CN201310523162.9A CN201310523162A CN104560169A CN 104560169 A CN104560169 A CN 104560169A CN 201310523162 A CN201310523162 A CN 201310523162A CN 104560169 A CN104560169 A CN 104560169A
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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
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1074—Vacuum distillates
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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
- 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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- General Chemical & Material Sciences (AREA)
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A hydrocracking method for producing heavy naphtha from a high-nitrogen stock comprises the following steps: mixing and heating a high-nitrogen raw oil and a hydrogen-rich gas, and enabling the heated mixture to enter a first reaction area to be subjected to hydrofining reaction and hydrocracking reaction; performing cooling, oil-gas separation and fractional distillation on the reactant flow to obtain light naphtha, heavy naphtha and tail oil distillates; and pressurizing the tail oil distillates, then mixing the pressurized tail oil distillates with recycle hydrogen, and enabling the mixture to enter a second reaction area to be subjected to hydrocracking reaction. In the second reaction area, the tail oil distillates which are difficult to convert can be all converted into naphtha distillates under the conditions of high airspeed and low severity. The method provided by the invention can be used for reducing the yield of products with relatively low added value, such as dry gas, liquefied gas and light naphtha, and improving the selectivity of heavy naphtha.
Description
Technical field
The invention belongs to a kind of method for hydrogen cracking obtaining low boiler cut hydrocarbon ils in the presence of hydrogen.More particularly, be a kind of method for hydrogen cracking producing heavy naphtha.
Background technology
Since the second half year in 2009, global economy manifests recovery sign, and the demand of worldwide petrochemical product is resumed the uptrend.Estimating to increase by 60% from present to the global demand of Chemicals in 2015 will from Asia, and the half of period Asia demand growth will from China.Benzene,toluene,xylene (being called for short BTX) is the basic material of petrochemical industry, and be the important component of stop bracket gasoline, the BTX needed for the whole world has nearly 70% to be from catalytic reforming, and heavy naphtha is the main raw material of catalytic reforming.Current, world's Petrochemical Enterprises faces a severe challenge: oil price Continued, and heavy inferior crude oil supply ratio increases; Petroleum chemicals demand is unbalanced, and part petroleum chemicals can not meet the demand of Economic development, and feed naphtha is in short supply.How to utilize the basic material of the acquisition petroleum chemicals of limited crude resources maximum, will the outstanding problem that future, for some time petrochemical industry faced be become.
Hydrocracking is one of main technique of heavy distillate deep processing, but prior art is mainly to produce clean fuel, carry out hydrocracking production by heavy distillate and obtain the clean fuels such as high-quality rocket engine fuel, diesel oil, the technology for voluminous heavy naphtha is relatively less.At present, fecund heavy naphtha approach mainly through improve reaction conversion ratio to increase yield, although simple raising depth of conversion improves heavy naphtha yield, the low value-added product yield also corresponding increases such as light naphthar, liquefied gas, dry gas, chemical hydrogen consumption also significantly rises, and economy is poor.The above last running of petroleum naphtha loops back cracking case can effective heavy naphtha yield, and all has clear improvement in heavy naphtha selectivity and chemical hydrogen consumption etc.But for the raw material that character is poor, the especially higher cycloalkyl wax oil of nitrogen content or wax tailings, still exists that heavy naphtha yield is low, poor selectivity, reaction severity are high, the high deficiency of chemical hydrogen consumption.Therefore developing new hydrocracking technology, cycloalkyl vacuum gas oil, the contour nitrogen heavy feed stock of coker gas oil to be converted into as far as possible the aromatic hydrocarbons material such as petroleum naphtha be one of effective way solving the shortage of petroleum chemicals basic material.
The invention provides a kind of method for hydrogen cracking processing high nitrogen heavy vacuum gas oil, coker gas wet goods heavy inferior raw material, adopt method provided by the present invention under the condition comparatively relaxed, the maximum of highly selective, low hydrogen consumption can obtain heavy naphtha.
CN 101210195A discloses a kind of method for hydrogen cracking by poor heavy raw material more producing chemical industry light oil, the method adopts preferred Hydrobon catalyst and hydrocracking catalyst, in single hop series connection once by processing the poor heavy raw material of high-sulfur height nitrogen under flow process, naphtha yield can reach about 35%.The method adopts once by flow process, and hold concurrently and produce part intermediate oil and tail oil, naphtha yield is restricted.
CN 101684415A discloses a kind of method for hydrogen cracking of producing chemical materials to maximum with low cost, the method flow process and the present invention is similar adopts Liang Ge hydrocracking reaction district.Hydrocracking section effluent, after being separated, loops back the second cracking reaction zone.The method also produces a large amount of tail oils as preparing ethylene by steam cracking device raw material while using aromatics production raw materials such as the whole convert naphtha of raw material such as decompressed wax oils.
Summary of the invention
The object of the invention is to provide a kind of method for hydrogen cracking producing heavy naphtha from high-nitrogen stock on the basis of existing technology.
Method provided by the invention comprises:
(1) heavy distillate enters the first reaction zone through heating after mixing with hydrogen-rich gas, after there is hydrofining reaction and hydrocracking reaction, reactant flow is after cooling, gas-oil separation, gained hydrogen-rich gas boosts Posterior circle to hydrofining reactor entrance and the second cracking reaction zone entrance through compressor, and uses as cold hydrogen.
(2) step (1) gained liquid obtains light naphthar, heavy naphtha and tail oil fraction through fractionation, and wherein tail oil fraction is mixed into the second hydrocracking reaction district and circulates after supercharging with recycle hydrogen;
(3) step (2) enters with the reaction effluent of step (1) and is separated and fractionating system.
(4) Hydrobon catalyst is the Hydrothermal Synthesis Hydrobon catalyst of high nitrogen removal performance newly developed.
Described heavy ends oil density is generally at 0.91g/cm
3above, usually at 0.92g/cm
3above; Aromaticity content generally more than 45%, usually more than 50%; Nitrogen content generally at 1500 more than μ g/g, usually at 2000 more than μ g/g.Heavy distillate comprises various hydrocarbon raw material, and typical raw material comprises one or more the mixture such as cycloalkyl vacuum gas oil (VGO), coker gas oil (CGO), deasphalted oil (DAO).
Adopt method provided by the invention to process cycloalkyl vacuum gas oil, the contour nitrogen heavy feed stock of coker gas oil of high nitrogen-containing, the reaction conditions that can comparatively relax, under relatively low chemical hydrogen consumption, the maximum of highly selective produces heavy naphtha.Gained naphtha fraction can reach more than 88% weight, wherein can reach more than 68% weight as production aroamtic hydrocarbon raw material heavy naphtha fraction yield.
Described reaction conditions is: hydrogen dividing potential drop 5.0 ~ 18.0MPa, temperature of reaction 300 ~ 430 DEG C, cumulative volume 0.1 ~ 8.0h
-1, hydrogen to oil volume ratio 300 ~ 3000Nm
3/ m
3.
The present invention adopts two-stage method operating process, wherein first paragraph process heavy distillate, the unconverted tail oil fraction of second segment process, two sections of parallel operations, shares high-low pressure separator and separation column and hydrogen gas system.First paragraph can adopt a reactor, loads the combination catalyst of Hydrobon catalyst and hydrocracking catalyst in reactor; First paragraph can also adopt two reactors in series flow processs, the first reactor charge Hydrobon catalyst, the second reactor charge hydrocracking catalyst.Second segment adopts a reactor, filling hydrocracking catalyst.
In hydrocracking process, the living source of cracking reaction is in acidic zeolite center, and the organic nitrogen compound in raw material is easily adsorbed on acid sites, causes cracking activity to reduce, even loss of activity.Therefore, for ensureing the stability of cracking catalyst activity, hydrofining reactor need be made to export the nitrogen content of oil lower than certain Con trolling index.The denitrification activity of Hydrobon catalyst is higher, and hydrofining reaction condition more relaxes.In other words, adopt the Hydrobon catalyst of high denitrification activity, the average reaction temperature of hydrofining reactor can be reduced or reduce the consumption of Hydrobon catalyst.
The Hydrobon catalyst that the present invention adopts hydro-thermal treatment preparation method thereof to obtain.This Hydrobon catalyst has strong nitrogen removal performance, and its preparation method is as follows:
With the porous support that a kind of aqueous impregnation is shaping, in closed reactor, hydrothermal treatment consists is carried out by flooding the mixture obtained, and solid product hydrothermal treatment consists obtained carries out drying, described porous support contains heat-resistant inorganic oxide and large pore molecular sieve, the described aqueous solution contain at least one containing the compound of group VIII metal and at least one containing the compound of group vib metal and containing or not containing solubility promoter.
Aforesaid method comprises and uses a kind of aqueous solution to carry out the porous support of dip forming, the described aqueous solution contain at least one containing the compound of group vib metal and at least one containing the compound of group VIII metal and containing or not containing solubility promoter.
In the described aqueous solution, the described concentration containing the compound of group vib metal and the compound containing group VIII metal, can meet concrete service requirements can make the content of group vib metal and group VIII metal in the catalyzer of final preparation and be as the criterion.Usually, when prepared according to the methods of the invention catalyzer is used for the hydrocracking of hydrocarbon ils, contain the total amount of the compound of group vib metal in the described aqueous solution and make containing the total amount of the compound of group VIII metal in the catalyzer of preparation, with oxide basis, the content of group vib metal is 10-50 % by weight, is preferably 10-45 % by weight; The content of group VIII metal is 1-10 % by weight, is preferably 1-7 % by weight; The content of porous support 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.When prepared according to the methods of the invention catalyzer is used for the hydrocracking of hydrocarbon ils, described group vib metal is preferably molybdenum and/or tungsten, and described group VIII metal is preferably cobalt and/or nickel.
Can by the compound containing group vib metal that this area is commonly used and containing the compound dissolution of group VIII metal in water, thus prepare the described aqueous solution.
The water-soluble cpds containing group vib metal that the described compound containing group vib metal can be commonly used for this area, the water-soluble cpds containing group VIII metal that the described compound containing group VIII metal can be commonly used for this area.
Particularly, the described compound containing group vib metal can be one or more in ammonium molybdate, ammonium paramolybdate, ammonium metawolframate, molybdenum oxide and Tungsten oxide 99.999.
The described compound containing group VIII metal can be the nitrate of group VIII metal, the muriate of group VIII metal, the vitriol of group VIII metal, the formate of group VIII metal, the acetate of group VIII metal, the phosphoric acid salt of group VIII metal, the Citrate trianion of group VIII metal, the oxalate of group VIII, the carbonate of group VIII metal, the subcarbonate of group VIII metal, the oxyhydroxide of group VIII metal, the phosphoric acid salt of group VIII metal, the phosphide of group VIII metal, the sulfide of group VIII metal, the aluminate of group VIII metal, the molybdate of group VIII metal, one or more in the tungstate of group VIII metal and the water-soluble oxide of group VIII metal, be preferably in the water-soluble oxide of the oxalate of group VIII metal, the nitrate of group VIII metal, the vitriol of group VIII metal, the acetate of group VIII metal, the muriate of group VIII metal, the carbonate of group VIII metal, the subcarbonate of group VIII metal, the oxyhydroxide of group VIII metal, the phosphoric acid salt of group VIII metal, the molybdate of group VIII metal, the tungstate of group VIII metal and group VIII metal one or more.
Particularly, the described compound containing group VIII metal can for but be not limited to: one or more in nickelous nitrate, single nickel salt, nickel acetate, basic nickel carbonate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol, Cobaltous diacetate, cobaltous dihydroxycarbonate, cobalt chloride and nickelous chloride.
The various solubility promoters that the described aqueous solution can also be commonly used containing this area, to improve the described compound containing group vib metal and the described solvability of compound in water containing group VIII metal; Or stablize the described aqueous solution, prevent precipitation.The various materials that can realize above-mentioned functions that described solubility promoter can be commonly used for this area, are not particularly limited.Such as, described solubility promoter can be one or more in phosphoric acid, citric acid and ammoniacal liquor.The present invention is not particularly limited for the concentration of described ammoniacal liquor, can be that the routine of this area is selected, be not particularly limited.The consumption of described solubility promoter can be the routine selection of this area, and usually, in the described aqueous solution, the content of described solubility promoter can be 1-10 % by weight.
According to method of the present invention, described porous support contains heat-resistant inorganic oxide and large pore molecular sieve.In the present invention, in described porous support, the content of described heat-resistant inorganic oxide and large pore molecular sieve can carry out appropriate selection according to the application scenario of the catalyzer of final preparation.When prepared according to the methods of the invention catalyzer is used for the hydrocracking of hydrocarbon ils, with the total amount of described porous support for benchmark, the content of described large pore molecular sieve can be 2-75 % by weight, is preferably 5-60 % by weight, be more preferably 5-40 % by weight, more preferably 5-30 % by weight; The content of described heat-resistant inorganic oxide can be 25-98 % by weight, is preferably 40-95 % by weight, is more preferably 60-95 % by weight, more preferably 70-95 % by weight.
According to the present invention, the various heat-resistant inorganic oxides that described heat-resistant inorganic oxide can be commonly used for this area.Usually, described heat-resistant inorganic oxide can be one or more in aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, aluminium oxide-silicon oxide, silica-magnesias, silica-zirconia, silica thoria, silica-berylias, silica-titania, silica-zirconia, titania-zirconia, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia and silica-alumina, zirconia.
Preferably, described heat-resistant inorganic oxide is aluminum oxide.The various aluminum oxide that described aluminum oxide can be commonly used for this area.Usually, described aluminum oxide can be one or more in gama-alumina, η-aluminum oxide, θ-aluminum oxide, δ-aluminum oxide and χ-aluminum oxide.According to the present invention, described aluminum oxide can also containing one or more the addO-on therapy be selected from titanium, magnesium, boron, zirconium, thorium, niobium and rare earth.In the present invention, the content of described addO-on therapy can carry out appropriate selection according to concrete application scenario, preferably, when prepared according to the methods of the invention catalyzer is used for the hydrocracking of hydrocarbon ils, in described aluminum oxide, the total amount of described addO-on therapy is 1-30 % by weight.According to the present invention, described aluminum oxide is preferably gama-alumina, or the gama-alumina containing one or more the addO-on therapy be 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.Such as, described large pore molecular sieve can for have faujusite structure zeolite molecular sieve, there is the zeolite structured zeolite molecular sieve of Beta and have in the zeolite molecular sieve of mordenite structure one or more.
Preferably, described large pore molecular sieve is y-type zeolite.
More preferably, described large pore molecular sieve be HY zeolite, rare-earth type Y zeolite (namely, REY zeolite), rare-earth type HY zeolite (namely, REHY zeolite), overstable gamma zeolite (namely, USY zeolite), one or more in rare-earth type overstable gamma zeolite (that is, REUSY zeolite), phosphorous y-type zeolite, 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 the mol ratio of described B acid and described L acid is for being greater than 0.9, and described zeolite molecular sieve is at 3685-3760cm
-1occur that at least one corresponds to the characteristic peak of silicone 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 silicone hydroxyl.
According to method of the present invention, described porous support can also contain the auxiliary agent that can improve the performance of the catalyzer of final preparation further of significant quantity, as phosphoric.The conventional various methods in this area can be adopted in described porous support to introduce described auxiliary agent, repeat no more herein.
According to the present invention, when adopting the method extruded to come shaping, described mixture can also contain extrusion aid and/or tackiness agent.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 condition of the formed body extruded being carried out roasting can be selected for the routine of this area.Such as, the temperature of described roasting can be 350-650 DEG C, is preferably 400-600 DEG C; The time of described roasting can be 2-6 hour, is preferably 3-5 hour.
Also comprise according to method of the present invention and carry out hydrothermal treatment consists by flooding the mixture obtained, described hydrothermal treatment consists is carried out under pressure is the condition of P0+ Δ P.
In the present invention, P0 is described porous support, the described compound containing group VIII metal, the described pressure containing the water in the compound of group vib metal, the solubility promoter containing or do not contain and the described aqueous solution and produce in hydrothermal treatment consists.
According to method of the present invention, in described hydrothermal treatment process, for carry out pressure in the encloses container of hydrothermal treatment consists except described porous support, the described compound containing group VIII metal, described contain group vib metal compound, containing or the solubility promoter that do not contain and the described aqueous solution in the pressure that produces of water except, also comprising Δ P, is 0.05-15MPa.Preferably, Δ P is 0.1-10MPa.From the angle of the internal pressure that catalytic activity and the described encloses container of the catalyzer of the final preparation of balance bear, Δ P is more preferably 0.2-8MPa.
In the present invention, pressure is all in gauge pressure.
The various methods that this area can be adopted to commonly use are carried out under pressure is the condition of P0+ Δ P to make described hydrothermal treatment consists.
In the present invention, the mode that described hydrothermal treatment consists is carried out under pressure is the condition of P0+ Δ P comprises: under the existence of volatile organic matter and non-active gas, carry out described hydrothermal treatment consists, the total pressure that total add-on of described volatile organic matter and non-active gas makes described volatile organic matter and non-active gas produce in hydrothermal treatment consists is Δ P.
Can adopt and make described hydrothermal treatment consists carry out under the existence of described volatile organic matter in various manners.Such as, described volatile organic matter can be added in the aqueous solution for flooding described porous support, thus described hydrothermal treatment consists is carried out under the existence of volatile organic matter; Also can by passing into described volatile organic matter in the encloses container carrying out described hydrothermal treatment consists, thus described hydrothermal treatment consists be carried out under the existence of volatile organic matter.From the angle of the catalytic activity of the catalyzer of raising preparation further, preferably in the encloses container carrying out described hydrothermal treatment consists, pass into volatile organic matter according to method of the present invention, thus described hydrothermal treatment consists is carried out under the existence of volatile organic matter.
In the present invention, described volatile organic matter can become the material of gaseous state by liquid state and/or can decompose the material of gas of generation under hydrothermal conditions for various under hydrothermal conditions.Such as, described volatile organic matter can be one or more organism in the polyoxyethylene glycol of 200-1500 for being selected from alcohol, acid, amine and number-average molecular weight.Preferably, described volatile organic matter is that to be selected from the fatty alcohol of C1-C30, the lipid acid of C2-C30, the aliphatic amide of C2-C30, the alkane of C6-C30 and number-average molecular weight be one or more in the polyoxyethylene glycol of 200-1500.More preferably, described volatile organic matter is that to be selected from the fatty alcohol of C1-C12, the lipid acid of C2-C10, the aliphatic amide of C2-C12, the alkane of C6-C12 and number-average molecular weight be one or more in the polyoxyethylene glycol of 200-1500.Further preferably, described volatile organic matter is selected from one or more in the alkane of the fatty alcohol of C1-C8, the lipid acid of C2-C5, the aliphatic amide of C2-C7 and C6-C11.
Particularly, described volatile organic matter can be one or more in the polyoxyethylene glycol being selected from n-propyl alcohol, Virahol, ethylene glycol, glycerol, triglycol, number-average molecular weight are 200-1500, Diethylene Glycol, butyleneglycol, acetic acid, toxilic acid, oxalic acid, nitrilotriacetic acid, 1,2-CDTA, tartrate, oxysuccinic acid, quadrol, hexane and isomer, heptane and isomer thereof, octane and isomer thereof and decane and isomer thereof.
In the present invention, described non-active gas refers in hydrothermal treatment process can not with porous support, there is chemically interactive gas containing the compound of group vib metal, compound, solubility promoter and the water containing group VIII metal, can be the conventional various non-active gas in this area.Preferably, described non-active gas is selected from the hydrocarbon of nitrogen, neutral element gas (such as: argon gas), carbonic acid gas, sulfur hexafluoride and C1-C5.
According to method of the present invention, the time of described hydrothermal treatment consists and temperature can be that the routine of this area is selected, as long as the 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.
Also comprise after mixture hydrothermal treatment consists obtained filters according to method of the present invention and carry out drying.The present invention is not particularly limited for the condition of described drying, can be that the routine of this area is selected.Usually, the condition of described drying comprises: temperature can be 100-300 DEG C, is preferably 100-280 DEG C, is more preferably 100-250 DEG C; Time can be 1-12 hour, is preferably 2-8 hour.
Can also comprise according to method of the present invention solid matter drying obtained and carry out roasting.The condition of described roasting can be the routine selection of this area.Usually, the condition of described roasting comprises: temperature can be 350-550 DEG C, is preferably 400-500 DEG C; Time can be 1-8 hour, is preferably 2-6 hour.
The composition of preferred Hydrobon catalyst: take catalyzer as benchmark, the heavy % of nickel oxide 1 ~ 10, molybdenum oxide and Tungsten oxide 99.999 sum are 10 ~ 50 heavy %, the heavy % of fluorine 1 ~ 10, the heavy % of Vanadium Pentoxide in FLAKES 0.5 ~ 8, and surplus is silica-alumina; Take carrier as benchmark, silica content is 2 ~ 45 heavy %, and alumina content is 55 ~ 98 heavy %.
Preferred Hydrobon catalyst, denitrification activity is more active than the hydrodenitrogenation catalyst of current advanced level high by about 30%, or when reaching identical denitrification percent, temperature of reaction can reduce by 8 ~ 10 DEG C, and aromatic saturation performance is also higher than advanced level catalyst for refining.Aromatic hydrocarbons hydrotreated lube base oil reaction be its open loop cracking must through step, the Hydrobon catalyst that the present invention adopts has excellent aromatic saturation performance, the hydrotreated lube base oil of the especially polycyclic aromatic hydrocarbons of aromatic hydrocarbons in stock oil can be promoted, for cracking zone provides the charging being easy to cracking reaction occurs, improve stock oil transformation efficiency.
Hydrocracking catalyst of the present invention a kind ofly to become carrier loaded at least one group VIII and the metal component of at least one group vib and the catalyzer of organic additive with alumina composite by zeolite, group VIII metal is selected from Co or/and Ni, group vib metal is selected from Mo or/and W, and described organic additive is selected from containing one or more in oxygen or nitrogenous organic compound.
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%, preferably 2.0 ~ 3.4%; Tungsten oxide content is 10 ~ 45%, preferably 20 ~ 34%.
Described zeolite is selected from one or more in faujusite, Beta zeolite, y-type zeolite and mordenite.
Preferred oxygen-containing organic compound is selected from one or more in Organic Alcohol, organic acid; Preferred organic compounds containing nitrogen is selected from one or more in organic amine, organic ammonium salt.Such as, oxygenatedchemicals can be ethylene glycol and triol, polyoxyethylene glycol (molecular weight is 200 ~ 2000), one or more in Diethylene Glycol, butyleneglycol, acetic acid, toxilic acid, oxalic acid, nitrilotriacetic acid, citric acid, tartrate; Itrogenous organic substance can be quadrol, ethylenediamine tetraacetic acid (EDTA) and ammonium salt thereof.
The preparation method of this hydrocracking catalyst is as follows: the predecessor of zeolite, aluminum oxide and/or aluminum oxide or what thing are mixed according to the ratio required by catalyzer, roll rear extrusion, make carrier after drying roasting.The active metal salt solution prepared according to a certain percentage and preferred organism are mixed with mixing solutions, are joined in solution by carrier and flood certain hour, elimination surplus solution, then dry, activation obtains finished catalyst.
Preferred hydrocracking catalyst selectivity of ring-opening is good, has the feature of high reactivity, high heavy naphtha yield.Compared with current high-caliber hydrocracking agent, when transformation efficiency is certain, the heavy naphtha fraction of higher yield can be obtained.In addition, the high cracking activity feature of preferred hydrocracking catalyst, can operate under more high-speed, more than 20% is improved than conventional hydrocracking catalyst Co., and catalyzer heap is than reduction by 15 ~ 30%, the loadings of both having saved catalyzer reduces reactor volume, again reduces the unit weight cost of catalyzer, thus reduces investment.
For ensureing the long-term operation of full scale plant, Hydrobon catalyst loads protective material, protective material is the group vib metal of load on amorphous alumina or silica-alumina supports or VIII non-precious metal catalyst or their combination.This type of protective material has larger pore volume and specific surface area.The volume ratio of protective material and Hydrobon catalyst is 0:100 ~ 20:100, preferred 5:100 ~ 15:100.
For preventing H
2s and the issuable alkene of cracking process react generation mercaptan sulfur further, a certain amount of Hydrobon catalyst is loaded bottom hydrocracking reactor, after this volume ratio of catalyst for refining and cracking catalyst is 5:100 ~ 20:100, preferred 10:100 ~ 15:100.The light-end products of gained of the present invention comprise light naphthar and heavy naphtha fraction.Light naphtha fraction can be used as gasoline blending component, also can be used as preparing ethylene by steam cracking raw material; Heavy naphtha fraction is rich in aromatic hydrocarbons, can directly as raw materials for catalytic reforming device.
Distinguishing feature of the present invention adopts the concept of reaction subregion for the treatment of high nitrogen heavy feed stock, the selectivity improving heavy naphtha.
In the first reaction zone by the high-performance Hydrobon catalyst described in employing, high nitrogen heavy feed stock can be made under the condition comparatively relaxed to reach the target of denitrogenation, aromatic saturation, first reaction zone setting unit cracking transformation function simultaneously, transform portion easy in stock oil is converted into heavy naphtha and more light component, this portioned product goes out device after being separated, to avoid, in second reaction zone, secondary cracking occurs, heavy naphtha is made to be converted into more light component.This reaction zone heavy naphtha yield controls 15% ~ 45%, reaction conditions relax, heavy naphtha yield and selectivity higher.First reaction zone effluent carries out circulation cracking through all the other the difficult transform portion after separation, fractionation in second reaction zone.
Second reaction zone is hydrocracking reaction district, and in this reaction zone reactive system, ammonia content is close to zero, without the performance of ammonia react environmental benefits in hydrocracking catalyst activity.Therefore, the second cracking reaction zone can realize, under high-speed, Low severity conditions, difficult transform portion more than naphtha fraction is all converted into naphtha fraction.Lower reaction severity means that cracking zone temperature of reaction is lower, and heat cracking reaction degree is also effectively controlled at a lower temperature, the product yield that the added values such as dry gas, liquefied gas and light naphthar are lower reduces to some extent, namely has higher heavy naphtha selectivity.The hydrocracking catalyst that two reaction zones loads can be the same or different, the hydrocracking catalyst type in differential responses district and reaction conditions are according to dissimilar raw material flexible operating, to ensure the production heavy naphtha of maximum under the condition relatively relaxed, and reduce gas and pumice productive rate, make reaction reach optimum.
In addition, the two-stage reaction adopted in the present invention shares separation system and hydrogen gas system can simplification of flowsheet greatly, reduces cost of equipment and energy consumption.Common recycle hydrogen can also reduce hydrocracking catalyst in second reaction zone and lose sulphur phenomenon, ensures that catalyst activity is stablized.
Accompanying drawing explanation
Accompanying drawing is a kind of method for hydrogen cracking schematic flow sheet producing heavy naphtha from high-nitrogen stock provided by the present invention.
Embodiment
Below in conjunction with accompanying drawing, method provided by the present invention is further detailed.
Accompanying drawing is a kind of schematic flow sheet producing the method for hydrogen cracking of heavy naphtha from high-nitrogen stock provided by the present invention.Some utility appliance such as interchanger etc. in figure does not mark, 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:
Stock oil mixes with the recycle hydrogen from pipeline 23 through pipeline 1, then the first reactor 2 is entered, desulfurization, denitrogenation and aromatic saturation reaction is there is in stock oil and hydrogen under Hydrobon catalyst effect, after reaction, stream passes via line 3 directly enters the second reactor 4, and oil, gas continue to react under hydrocracking catalyst effect.The generation logistics of the second reactor enters high-pressure separator 6 through pipeline 5,19 successively and carries out gas-oil separation, for preventing ammonium salt crystallization from separating out blocking pipeline, exporting wash through pipeline 18 water filling at the second reactor 4.High-pressure separator 6 top gas enters circulating hydrogen compressor 21 through pipeline 20, mixes after hydrogen-rich gas supercharging with the new hydrogen supplemented through pipeline 22, returns the first reactor 2 and the 3rd reactor 16 recycles through pipeline 23.The isolated liquid through line of high-pressure separator 67 enters light pressure separator 8 and carries out further gas-oil separation, the isolated gas of light pressure separator 8 is through pipeline 9 emptying, isolated liquid through line 10 enters separation column 11, the isolated lighter hydrocarbons of tower top, light naphtha fraction are through pipeline 12 caterpillar, and top side line extracts heavy naphtha fraction out through pipeline 13.Tail oil fraction more than heavy naphtha can extract separation column out through pipeline 14, also the 3rd reactor 16 can be mixed into through pipeline 15 and the recycle hydrogen from pipeline 23 after supercharging, oil, gas carries out secondary reaction under the effect of hydrocracking catalyst, enters separation system after the generation stream passes via line 17 of the 3rd reactor 16 mixes with the generation logistics from the second reactor 4 through pipeline 19.
The following examples will be further described present method, but therefore not limit present method.
In embodiment use the commercial grades of hydrocracking catalyst for RHC-5, in comparative example, the commercial grades of Hydrobon catalyst used is RN-32V, is Sinopec catalyzer branch office Chang Ling catalyst plant and produces.In embodiment, Hydrobon catalyst used is 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 is produced, and commodity are called PSRY, and lattice constant is
phosphorus content is 5 % by weight), 700 grams of butt pseudo-boehmites (Shandong Aluminum Plant produces, trade(brand)name SD powder, and contents on dry basis is 69 % by weight) and 30 grams of sesbania powder mix, and are extruded into forcing machine the trilobal bar that circumscribed circle diameter is 1.6 millimeters.By the formed body extruded 120 DEG C of dryings 5 hours, then 550 DEG C of roastings 3 hours, obtained carrier S 3.In carrier S 3, the content of large pore molecular sieve is 30 % by weight, and the content of aluminum oxide is 70 % by weight.
Join in 150 ml waters by 20 grams of basic nickel carbonates, add 8 grams of phosphoric acid with stirring, heated and stirred is dissolved, and adds 12 grams of ammonium molybdates and 110 grams of ammonium metawolframates respectively, after dissolving, add water and be settled to 200 milliliters with stirring.Adopt the above-mentioned aqueous impregnation of the method for excessive dipping 100 grams of carrier S 3, dipping time is 0.5 hour.Autoclave is placed in by flooding the mixture obtained, and add 15 milliliters of Virahols, carry out hydrothermal treatment consists, the condition of hydrothermal treatment consists comprises: temperature is 100 DEG C, time is 24 hours, in autoclave, pass into argon gas in hydrothermal treatment process makes the pressure in autoclave be 3.3MPa, wherein, and P
0=0.3MPa, Δ P=3.0MPa.Mixture hydrothermal treatment consists obtained is cooled to room temperature, after filtration, by the solid that obtains 120 DEG C of dryings 2 hours, then 200 DEG C dry 3 hours again, obtain catalyst A, consisting of of catalyst A, be benchmark with monolith, with oxide basis, tungsten is 30.4 % by weight, molybdenum is 3.1 % by weight, and nickel is 4.2 % by weight.
Comparative example 1
With one high nitrogen heavy VGO for stock oil A, its feedstock property is as table 1.Adopt catalyzer provided by the invention, stock oil goes out product enter high-pressure separator after refining reaction device, cracking case after, and the above cut of heavy naphtha is without circulation.Experimental result lists in table 2-table 4.
Comparative example 2
With the mixing raw material oil B containing VGO and CGO for raw material, adopt two sections of conventional boiling ranges, Hydrobon catalyst is only loaded in the first reaction zone, and hydrocracking catalyst is only loaded in second reaction zone, product is after being separated, and the above cut of heavy naphtha loops back second reaction zone and realizes full conversion.Experimental result lists in table 5-table 7.
Embodiment 1
The present embodiment adopts the stock oil identical with comparative example 1, carries out hydrocracking tests with Hydrobon catalyst A provided by the present invention and technical process, and experimental result lists in table 2-table 4.
As can be seen from the table, in the heavy naphtha situation of production same amount, adopt method provided by the present invention with once by compared with flow process, required hydrogen consumption is less, and heavy naphtha virtue is dived higher.
Embodiment 2
The present embodiment adopts the mixing raw material oil B containing VGO and CGO, carries out hydrocracking tests with catalyzer provided by the present invention and technical process, and experimental result lists in table 5-table 7.
As can be seen from the table, adopting method provided by the present invention can be down to minimum by the yield of tail oil under the condition of hydrogen dividing potential drop 13.0MPa, is 0; And maximum production obtains light naphthar and heavy naphtha product, total recovery reaches 89 heavy more than %.Show present method can under the condition relatively relaxed the production petroleum naphtha of maximum.
Table 1, stock oil character
| Stock oil title | A | B |
| Density, g/cm 3 | 0.921 | 0.930 |
| 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 conditions
Table 3, comparative example 1 and embodiment 1 product slates data
| Comparative example 1 | Embodiment 1 | |
| Chemical hydrogen consumption, heavy % | 2.30 | 2.23 |
| Product slates, heavy % | ||
| H 2S | 2.66 | 2.66 |
| NH 3 | 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 slates data
| Project | Comparative example 2 | Embodiment 2 |
| Chemical hydrogen consumption, heavy % | 3.37 | 3.30 |
| Product slates, heavy % | ||
| H 2S | 2.87 | 2.87 |
| NH 3 | 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 (18)
1. produce a method for hydrogen cracking for heavy naphtha from high-nitrogen stock, comprising:
(1) heavy distillate enters the first reaction zone through heating after mixing with hydrogen-rich gas, after there is hydrofining reaction and hydrocracking reaction, reactant flow is after cooling, gas-oil separation, gained hydrogen-rich gas boosts Posterior circle to hydrofining reactor entrance and second reaction zone entrance through compressor, and uses as cold hydrogen;
(2) step (1) gained liquid obtains light naphthar, heavy naphtha and tail oil fraction through fractionation, and wherein tail oil fraction is mixed into second reaction zone and carries out hydrocracking reaction after supercharging with recycle hydrogen;
(3) step (2) enters same separation system and fractionating system with the reaction effluent of step (1);
First reaction zone and second reaction zone are parallel mode of operation.
2. in accordance with the method for claim 1, it is characterized in that, described heavy ends oil density is at least 0.91g/cm
3above, aromaticity 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 ends oil density is at least 0.92g/cm
3above, aromaticity content is greater than more than 50%, and nitrogen content is greater than 2000 μ g/g.
4. according to the method described in Claims 2 or 3, it is characterized in that, heavy distillate is selected from one or more in cycloalkyl vacuum gas oil, coker gas oil, deasphalted oil.
5. in accordance with the method for claim 1, it is characterized in that, described reaction conditions is: hydrogen dividing potential drop 5.0 ~ 18.0MPa, temperature of reaction 300 ~ 430 DEG C, cumulative volume 0.1 ~ 8.0h
-1, hydrogen to oil volume ratio 300 ~ 3000Nm
3/ m
3.
6. in accordance with the method for claim 1, it is characterized in that, adopt a reactor in the first reaction zone, in reactor, load Hydrobon catalyst and hydrocracking catalyst successively; Or, adopt two reactors in series flow processs in the first reaction zone, the first reactor charge Hydrobon catalyst, the second reactor charge hydrocracking catalyst.
7. in accordance with the method for claim 6, it is characterized in that, the Hydrobon catalyst that the present invention adopts hydro-thermal treatment preparation method thereof to obtain, with the porous support that a kind of aqueous impregnation is shaping, in closed reactor, hydrothermal treatment consists is carried out by flooding the mixture obtained, and solid product hydrothermal treatment consists obtained carries out drying, described porous support contains heat-resistant inorganic oxide and large pore molecular sieve, the described aqueous solution contain at least one containing the compound of group VIII metal and at least one containing the compound of group vib metal and containing or not containing solubility promoter.
8. in accordance with the method for claim 7, it is characterized in that, contain the total amount of the compound of group vib metal in the described aqueous solution and make containing the total amount of the compound of group VIII metal in the catalyzer of preparation, with oxide basis, the content of group vib metal is 10-50 % by weight, the content of group VIII metal is 1-10 % by weight, and the content of porous support is 40-89 % by weight.
9. in accordance with the method for claim 8, it is characterized in that, contain the total amount of the compound of group vib metal in the described aqueous solution and make containing the total amount of the compound of group VIII metal in the catalyzer of preparation, with oxide basis, the content of group vib metal is for being 10-45 % by weight; The content of group VIII metal is 1-7 % by weight; The content of porous support is 48-89 % by weight.
10. in accordance with the method for claim 7, it is characterized in that, described group vib metal is preferably molybdenum and/or tungsten, and described group VIII metal is preferably cobalt and/or nickel.
11. in accordance with the method for claim 10, it is characterized in that, the described compound containing group vib metal be selected from ammonium molybdate, ammonium paramolybdate, ammonium metawolframate, molybdenum oxide and Tungsten oxide 99.999 one or more.
12. in accordance with the method for claim 10, it is characterized in that, the described compound containing group VIII metal be selected from nickelous nitrate, single nickel salt, nickel acetate, basic nickel carbonate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol, Cobaltous diacetate, cobaltous dihydroxycarbonate, cobalt chloride and nickelous chloride one or more.
13. in accordance with the method for claim 7, it is characterized in that, described solubility promoter be selected from phosphoric acid, citric acid and ammoniacal liquor one or more, in the described aqueous solution, the content of described solubility promoter is 1-10 % by weight.
14. in accordance with the method for claim 7, it is characterized in that, described porous support contains heat-resistant inorganic oxide and large pore molecular sieve, with the total amount of described porous support for benchmark, the content of described large pore molecular sieve is 2-75 % by weight, and the content of described heat-resistant inorganic oxide is 25-98 % by weight.
15. in accordance with the method for claim 7, it is characterized in that, described porous support contains heat-resistant inorganic oxide and large pore molecular sieve, and with the total amount of described porous support for benchmark, the content of described large pore molecular sieve is 5-40 % by weight; The content of described heat-resistant inorganic oxide is 60-95 % by weight.
16. in accordance with the method for claim 7, it is characterized in that, heat-resistant inorganic oxide refers under oxygen or oxygen-containing atmosphere, and decomposition temperature is not less than the inorganic oxygen-containing compound of 300 DEG C.
17. in accordance with the method for claim 7, it is characterized in that, described large pore molecular sieve refers to the zeolite molecular sieve with twelve-ring pore structure.
18. in accordance with the method for claim 7, it is characterized in that, also comprise according to method of the present invention and carry out hydrothermal treatment consists by flooding the mixture obtained, described hydrothermal treatment consists is carried out under pressure is the condition of P0+ Δ P, P0 is described porous support, the described compound containing group VIII metal, the described pressure containing the water in the compound of group vib metal, the solubility promoter containing or do not contain and the described aqueous solution and produce in hydrothermal treatment consists, and Δ P is 0.05-15MPa.
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| CN109988629A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | A kind of wax oil hydrogenation cracking method and system |
| CN109988607A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | Flexible two-stage reforming technique |
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| CN109988629A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | A kind of wax oil hydrogenation cracking method and system |
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