CN1712499A - Diesel production from hydrogenation upgrading isomerizing pour-point reduction - Google Patents
Diesel production from hydrogenation upgrading isomerizing pour-point reduction Download PDFInfo
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- CN1712499A CN1712499A CN 200410020796 CN200410020796A CN1712499A CN 1712499 A CN1712499 A CN 1712499A CN 200410020796 CN200410020796 CN 200410020796 CN 200410020796 A CN200410020796 A CN 200410020796A CN 1712499 A CN1712499 A CN 1712499A
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- 238000005984 hydrogenation reaction Methods 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 230000009467 reduction Effects 0.000 title description 3
- 239000002808 molecular sieve Substances 0.000 claims abstract description 84
- 238000000034 method Methods 0.000 claims abstract description 68
- 239000002283 diesel fuel Substances 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- 230000008569 process Effects 0.000 claims abstract description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 26
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011148 porous material Substances 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 16
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-UHFFFAOYSA-N 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 13
- 230000004048 modification Effects 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- 238000010306 acid treatment Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
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- 238000005406 washing Methods 0.000 claims description 8
- 238000010335 hydrothermal treatment Methods 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
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- 150000003863 ammonium salts Chemical group 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 5
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- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229960001866 silicon dioxide Drugs 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
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- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
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- 239000011707 mineral Substances 0.000 claims description 2
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
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- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Production of hydrogenated and pour-point reducing modified isomerization diesel oil is carried out by using fraction oil as raw material from one-stage or series process flow, passing fraction oil raw material and hydrogen gas into catalyst bed which consists of beta molecular sieve 1-9wt%, and obtaining clean high-quality diesel product and naphtha product with low sulfur nitrogen and high arene content. The beta molecular sieve has small crystal grain, low acidity, high silica-alumina ratio and crystallinity. It achieves simple process, higher productivity and less impurities, and improves density and freezing point.
Description
Technical field
The present invention relates to a kind of hydro-upgrading isomerization-visbreaking and produce the method for diesel oil, select catalyzer for use, produce the method for low-coagulation diesel oil with distillate with strong isomery function.
Background technology
The sustainable development of national economy has driven the fast development of automotive industry and transportation, and especially the diesel car rate of growth is faster, has also brought motor vehicle exhaust to atmospheric pollution problem simultaneously.For effectively control motor vehicle exhaust; the human ecotope of depending on for existence of protection; countries in the world especially developed country when motor car engine and exhaust treatment system etc. thereof is updated; the diesel product quality has also been proposed more and more high requirement, and leading indicator comprises indexs such as sulphur, nitrogen content, aromaticity content, cetane value, density, condensation point, T95.Therefore, how to use alap investment and process cost, production environment close friend's automobile-used oil product satisfies harsh day by day market demands, has become the current problem that needs to be resolved hurrily of oil refining enterprise.
CN 1171430A has introduced a kind of employing middle pressure hydrocracking method, though can increase substantially diesel-fuel cetane number, but owing to there is some diesel oil to be converted to naphtha fraction, diesel product yield is reduced, this market requirement with current raising diesel and gasoline ratio contradicts, so it is applied and is subjected to certain limitation.US 6,129, and 835 have introduced the conventional hydrofining technology that adopts, though impurity such as energy effective elimination sulphur, nitrogen obviously improve the color and the stability of diesel product, and keep very high diesel yield, diesel product cetane value amplification is limited.The hydrodewaxing technology that CN 1061679C introduces is the shape cracking technology process of selecting of carrying out under hydrogen and the middle pressure condition facing.It utilizes the pore passage structure of particular molecule sieve catalyst uniqueness and suitable acid sites, and the contour condensation point component of the normal paraffin in the diesel feed is carried out selective splitting, and to reduce the zero pour of diesel product, the while by-product is gasoline and C partly
3, C
4Lighter hydrocarbons.Adopt this technology, the maximum pour point depression amplitude of diesel oil can reach more than 50 ℃, and can be by adjusting the pour point depression amplitude of controlling reaction temperature diesel oil.But because the hydrogenation ability of used Hydrodewaxing catalyst is very weak, do not remove the impurity such as sulphur nitrogen in the oil product substantially, cause therefore that low-coagulation diesel oil product foreign matter content is higher, oxidation stability is relatively poor.CN1257107A has introduced hydrogenation pour point depression technology.This technology adopts hydrofining-hydrodewaxing combination process flow process, by the hydrogenation pre-refining is carried out in charging, not only improved hydrodewaxing section feeding quality, improved adaptability to stock oil, prolonged the running period of device, and alleviated operational condition greatly, and the purpose quality product is greatly improved.Adopt hydrogenation pour point depression technology to produce low-coagulation diesel oil, though can reduce the zero pour of diesel product significantly, but compare still with the requirement of producing clean fuel and to come with some shortcomings, as: can not obviously improve the diesel product cetane value, can not significantly reduce diesel product density and T95, diesel product yield is lower, and by-product naphtha olefins content is higher.
US5,030,780 uses the catalyst treatment diesel oil contain Y zeolite and amorphous silicon aluminium, mainly the aromatic hydrocarbons in the diesel oil is carried out saturated, but limited to other improved performances such as cetane value, condensation points.CN1156752A discloses a kind of diesel modifying technology, uses hydrocracking catalyst, under the condition of a certain amount of nitrogen of control, makes the aromatic hydrocarbons in the diesel oil carry out ring-opening reaction, can improve diesel-fuel cetane number greatly, but can not effectively reduce the condensation point of diesel oil.US4,419,220 use the catalyzer that contains precious metal and beta-molecular sieve that content of wax hydrocarbon material is carried out isomerization dewaxing handles, because precious metals such as use platinum, impurity such as sulphur, nitrogen can make precious metal poison and inactivation.Though adopt ion-exchange techniques that precious metal is replaced molecular sieve structure inside, can suppress precious metal to a certain extent and poison, anti-impurity ability is still very limited.So adopt the catalyzer that contains precious metal, generally need earlier that impurity removals such as the sulphur in the raw material, nitrogen is clean.This needs to use complicated two-stage method technology on technological process, the equipment that needs is more, and cost of investment and process cost are all higher.In addition, this technology is only emphasized the reduction to condensation point, does not relate to the improvement of other index, and selected condition and catalyzer all are the basis from helping pour point depression.And the cost of noble metal catalyst is also higher.US5,011,593 introduces a kind of sweetening process that is used for sulphur and the higher raw material of aromaticity content, uses the catalyzer contain beta-molecular sieve, and using the sulphur content of raw material is 0.5～5.0wt%, more than the aromaticity content 50wt%, as the light cycle oil of catalytic cracking etc.This patent is only emphasized the sweetening effectiveness to raw material, does not consider other performance index.In order to realize its specific objective, the catalyzer that uses contains beta-molecular sieve 20～70wt%, and (described other binding agent of specification sheets and hydrogenation metal component concentration are 30～80wt%), because beta-molecular sieve has certain acidity, has cracking performance, when content is higher, have higher cracking conversion rate, its result and mild hydrocracking are suitable.And, use the bigger beta-molecular sieve of crystal grain, can make second pyrolysis more, the yield of final diesel oil reduces.As described in its specification sheets, be 95% o'clock at desulfurization degree, former cut range product yield will be lower than 85wt%.
In sum, prior art all can not comprehensively improve the every performance index of diesel oil, the clean diesel of production high-quality simply.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of can comprehensively improve diesel oil multinomial performance index, to greatest extent produce fine-quality diesel oil hydrotreatment (hydro-upgrading isomerization-visbreaking) method.
The method of hydrotreatment of the present invention (hydro-upgrading isomerization-visbreaking) production fine-quality diesel oil is specific as follows: with the distillate is raw material, adopt single hop or series process flow, under optimum conditions, distillate feedstock and hydrogen is by beds, obtains cleaning fine-quality diesel oil product and a small amount of sulphur nitrogen content is low, arene underwater content is high naphtha product.Described beds comprises a hydrotreating catalyst bed that contains beta-molecular sieve at least, hydrotreating catalyst comprises beta-molecular sieve, refractory porous oxide, group vib and the VIII family metal oxide of amorphous aluminum silicide, modification, weight percent with catalyzer is a benchmark, contain modified beta molecular sieve 1w%～9w% in the catalyzer, the silicon-dioxide of modified beta molecular sieve/aluminium sesquioxide weight ratio is 50～90, average grain size is 0.1～0.5 micron, infrared acidity 0.1～0.4mmol/g.
The inventive method can adopt the single hop hydroprocessing technique, also can adopt the serial hydrogenation treatment process.The single hop hydroprocessing technique refers to use a kind of type catalyst (protective material etc. can be arranged).Series process flow refers to that dissimilar catalyzer have formed the two or several different reaction zone of order, can in a reactor, load dissimilar catalyzer, form the cascade reaction district, also can use and use dissimilar catalyzer in two or more tandem reactors, form the cascade reaction district.In the serial hydrogenation treatment process, raw material is at first by conventional Hydrobon catalyst bed, then by containing the hydrotreating catalyst bed of beta-molecular sieve.The single hop hydroprocessing technique uses the hydrotreating catalyst that contains beta-molecular sieve.The reaction conditions of raw material when containing the hydrotreating catalyst bed of beta-molecular sieve is generally reaction pressure 4.0～18.0MPa, hydrogen to oil volume ratio 300～1500, volume space velocity 0.4～10.0h
-1, temperature of reaction 290～430.Being preferably reaction conditions is reaction pressure 5.0～18.0MPa, hydrogen to oil volume ratio 500～1500, volume space velocity 0.5～4.0h
-1, 300～420 ℃ of temperature of reaction.If adopt the serial hydrogenation treatment process, raw material can be identical with the condition by the beta-molecular sieve hydrotreating catalyst by the condition of conventional Hydrobon catalyst bed reaction zone, also can be different.Can be conventional hydroprocessing condition, general reaction conditions be reaction pressure 0.5～18.0MPa, temperature 230～430, hydrogen to oil volume ratio 200～1500, volume space velocity 0.5～10.0h
-1, preferably in by the operational condition scope that contains beta-molecular sieve hydrotreating catalyst bed.
The hydrotreating catalyst that contains beta-molecular sieve comprises the beta-molecular sieve of amorphous aluminum silicide, modification, refractory porous oxide, group vib and VIII family metal oxide etc.Weight percent with catalyzer is a benchmark, and each components contents is in the catalyzer: amorphous aluminum silicide generally is 29w%～52w%, better is 32w%～47w%; Modified beta molecular sieve generally is 1w%～9w%, better is 2w%～8w%; The group vib metal is generally 15w%～30w% in oxide compound, is preferably 18w%～26w%; The group VIII metal is generally 3w%～9w% in oxide compound, is preferably 5w%～7w%.The porous refractory oxide, as in aluminum oxide, titanium oxide, zirconium white, boron oxide and the above-mentioned elements compounding oxide compound etc. one or more, preferred aluminum oxide.Porous refractory oxide content is generally 0w%～45w%, is preferably 20w%～35w%.As containing macroporous aluminium oxide and aperture alumina adhesive, macroporous aluminium oxide is generally 0w%～22w%, is preferably 4w%～14w%; Little porous aluminum oxide is generally 0w%～23w%, is preferably 16w%～22w%.The specific surface area of catalyzer is 160～230m
2/ g, pore volume are 0.32～0.45ml/g.
The character of described modified beta molecular sieve is: its silicon-dioxide/aluminium sesquioxide weight ratio is generally 50～90, be preferably 60～80, degree of crystallinity is generally 90～110, preferably 100～110, average grain size is generally 0.1～0.5 micron, preferably 0.1～0.3 micron, specific surface area 400～750m
2/ g, preferably 500～600m
2/ g, pore volume 0.25～0.50ml/g, 0.3～0.4ml/g preferably, Na
2O content is less than 0.10w%, preferably less than 0.05w%, and infrared acidity 0.1～0.4mmol/g, best 0.2～0.3mmol/g, the secondary pore pore volume of 2～10nm accounts for 30～60% of total pore volume.
SiO in the described amorphous aluminum silicide
2Content be 20w%～75w%, be preferably 35w%～60w%.The pore volume of amorphous aluminum silicide is 0.5～1.1ml/g, is preferably 0.6～0.8ml/g.Specific surface area is 200～500m
2/ g is preferably 280～500m
2/ g.
The macroporous aluminium oxide pore volume is 0.6～1.2ml/g, is preferably 0.8～1.2ml/g, and specific surface area is 200～550m
2/ g is preferably 300～500m
2/ g.Aperture aluminum oxide pore volume is 0.3～0.5ml/g, and specific surface area is 180～350m
2/ g.
The group vib metal is generally W and/or Mo, and the group VIII metal is generally Ni and/or Co.
The present invention takes all factors into consideration the many index requirement of clean diesel, selects suitable technical process, optimizes concrete processing condition, determines suitable catalyzer, can be the fine-quality diesel oil product with poor-quality diesel-oil by cut fraction raw material time processing.The inventive method can remove the impurity such as sulfide, nitride, oxide compound, organic acid, phenol, alkene and aromatic hydrocarbons in the raw material, the part selective opening of cyclic paraffins can also be reduced viscosity, density by a relatively large margin; Heavy component in the raw material is carried out the hydrocracking of appropriateness, can make the final boiling point reach, reduce T95, but less to the diesel yield influence; The contour condensation point component of normal paraffin in the raw material is carried out isomerization-visbreaking, significantly reduce the condensation point and the cold filter clogging temperature of diesel oil.Adopt the present invention program, sulphur, nitrogen decreasing ratio can reach more than 99%, and cetane value can improve about 10 units, and condensation point, T95, density, aromaticity content etc. all have reduction significantly.Simultaneously, diesel yield is higher, and generally at 88w%～99w%, under the representative condition, diesel yield is about 96w%, and by-product is the petroleum naphtha with higher arene underwater content.The inventive method also has advantages such as running is stable, flow process is simple, investment is low, the catalyst runs cycle is long.The catalyzer that the inventive method is selected not only has good use properties, owing to use the non-noble metal hydrogenation component, the cost of catalyzer is low simultaneously, catalyzer adaptability is strong, good stability applicable to single hop or series process flow, and need not two sections complicated flow processs.The inventive method has bigger flexibility of operation, can fine adaptation market to the seasonal variation of product demand, thereby can obtain good economic benefits.
The catalyzer that the present invention selects is main acidic components with amorphous aluminum silicide, the beta-molecular sieve that adds a small amount of special modification is second acidic components, by compound and optimize this two kinds of catalytic materials, promptly given full play to its performance characteristics separately, produced concerted catalysis effect preferably again, make catalyzer of the present invention when activity improves, have good selective opening of cyclic paraffins, isomerization of paraffinic hydrocarbons, the hydrocracking of last running appropriateness again, aromatic hydrocarbons is saturated and heteroatoms removes performance.The beta-molecular sieve acidity of using is suitable, the acid site number is less, but is evenly distributed, and the degree of crystallinity height, crystal grain is little and even, has certain secondary pore.Because the beta-molecular sieve particle diameter is less, the time that reactant molecule is stopped in molecular sieve pore passage shortens greatly, has reduced the probability of secondary reaction, has kept the yield of purpose product diesel oil well; But too little this reaction process that also is unfavorable for of particle diameter is important so select suitable molecular sieve particle diameter.This effect be general molecular sieve only by control itself acidity inaccessible.Secondary pore can make the resultant of reaction spread smoothly, and minimizing second pyrolysis, raising diesel yield are had very favourable effect.In addition, the modified beta molecular sieve that the present invention selects has suitable splitting action and good isomerization to the long side chain alkyl of long chain alkane and aromatic hydrocarbons, naphthenic hydrocarbon, can when keeping high diesel yield, reduce the condensation point of diesel oil distillate by a relatively large margin, reach the effect of volume increase low-coagulation diesel oil.
Embodiment
The present invention can adopt a segment process flow process, also can adopt series process flow.Series process flow is more reasonable economically, more stable in operation (series connection described in the present invention is corresponding with single hop, rather than with in parallel corresponding, parallel connection is equivalent to enlarge the reactor scale, and nature is in protection domain of the present invention).The beta-molecular sieve hydrotreating catalyst that contains that uses in single hop technology and the tandem process can be that (character comprises beta-molecular sieve content to the character homogeneous, beta-molecular sieve character, the reactive metal kind, active metallic content, kind of carrier, one or more in the carrier character etc.) a kind of catalyzer, also several catalyzer of above-mentioned different in kind, as along the raw material flow direction, use the catalyzer of several beta-molecular sieve content increases, or use the acid catalyzer that increases of several beta-molecular sieves etc.This is more favourable to giving full play to catalyst performance.
The modified beta molecular sieve that contains in the beta-molecular sieve catalyzer that technology of the present invention is used is to make by new synthesis modification method, and the key step of modification comprises:
(1) the beta-molecular sieve slurries after the crystallization directly carry out ammonium exchange, filtration, washing, drying and roasting;
(2) beta-molecular sieve that takes off behind the ammonium of roasting carries out acid treatment;
(3) the intact beta-molecular sieve of acid treatment carries out hydrothermal treatment consists again.
Beta-molecular sieve after the above-mentioned crystallization generally is to be template with organic ammonium (as tetraethyl ammonium hydroxide), uses the hydrothermal crystallization method synthetic.Its SiO
2/ Al
2O
3Weight ratio is generally 25～30, Na
2The content of O is 3.0w%～4.0w%.Beta-molecular sieve slurries after the crystallization directly carry out the ammonium salt exchange, and the concentration of ammonium salt in slurries is 0.5～5.0mol/l, and several is carried out in the ammonium exchange, make Na in the molecular sieve of exchange back
2The O weight content is not more than 0.5%, and general ammonium exchange 1～4 time can reach requirement.Beta-molecular sieve after the ammonium salt exchange filters, washes, drying and roasting, and wherein maturing temperature is controlled at 450 ℃～650 ℃, and the time is 5.0～15.0 hours.The beta-molecular sieve that roasting is taken off behind the ammonium carries out acid treatment, filters, and wherein acid treatment condition is for being that the mineral acid of 0.1～5.0mol/l is carrying out acid treatment with concentration under abundant agitation condition, 20 ℃～100 ℃ of treatment temps, and the treatment time is 0.5～5.0 hour.The intact beta-molecular sieve of acid treatment carries out pressurized thermal water to be handled, the hydrothermal treatment consists condition for 100% water vapor at 500 ℃～800 ℃, be preferably 550 ℃～700 ℃, system pressure is 0.05～1.0MPa, be preferably 0.1～0.5MPa, handled preferably 1～2 hour 0.5～5.0 hour.
Catalyzer adopts conventional pickling process production, with beta-molecular sieve, porous refractory oxide, tackiness agent and the extrusion aid mixing of amorphous aluminum silicide, modification, and extruded moulding, drying, roasting, the impregnating metal component, dry, roasting prepares final catalyzer.
Further specify Preparation of catalysts method of the present invention and use properties below by embodiment.
Distillate feedstock can be the various raw materials that contain diesel oil distillate, mainly comprise the distillate feedstock that contains straight(-run) diesel distillate and/or secondary processing diesel oil cut, as straight-run diesel oil, straight run light wax oil, catalytic diesel oil, coker gas oil etc., can also use the diesel oil through hydrotreatment to be raw material, and one or more mixing oil in the above-mentioned raw materials oil.Also can contain part gasoline fraction and heavy ends.The raw material that uses among the embodiment is seen
Table 2.
Series process flow first reaction zone uses the commercial Hydrobon catalyst FH-98 of Wenzhou Hua Hua group company production or the commercial Hydrobon catalyst 3996 that the Fushun Petrochemical Company catalyst plant is produced, and character sees Table 3.
Embodiment 1
With 227.1 gram amorphous aluminum silicide (SiO
2Content be 45w%, pore volume is 0.75ml/g, specific surface area is 390m
2/ g), 18.8 the gram modifications beta-molecular sieves, 65.8 the gram macroporous aluminium oxides (pore volume is 1.0ml/g, and specific surface area is 460m
2/ g) put into rolling machine, mixed grind 30 minutes, (containing pore volume is that 0.4ml/g, specific surface area are 280m to add 288.5 gram tackiness agents then
2The aperture aluminum oxide 107.1g of/g, HNO
3With alumina molar ratio be 0.3), rolled 30 minutes, add 60 ml waters afterwards, continue to roll to can squeezing paste, extrusion is extruded bar 110 ℃ of dryings 6 hours.Dried strip temperature programming to 580 ℃ roasting 4 hours gets carrier.Carrier is with the steeping fluid room temperature dipping of tungstenic and nickel 2 hours, 120 ℃ of dryings 6 hours, 480 ℃ of roastings of temperature programming 4 hours, catalyst A.Physico-chemical property sees Table 1.
Wherein the beta-molecular sieve character of modification is: molecular sieve SiO
2/ Al
2O
3Weight ratio 70, relative crystallinity are 107, specific surface 570m
2/ g, infrared acidity 0.25mmol/g, the secondary pore pore volume of 2～10nm accounts for 45% of total pore volume, average crystal grain diameter 0.2 μ m.Concrete modifying process is as follows: get industrial synthetic SiO
2/ Al
2O
3Weight ratio 25, Na
2The Na beta-molecular sieve slurries 2000ml of O 3.65w%, contain solid phase 400g (in butt), with water purification solid-to-liquid ratio is diluted to 1: 10, preparation 2.0M ammonium nitrate solution stirred, is warming up to 85 ℃ and constant temperature 2 hours, was cooled to 50 ℃ of filtrations, wet cake carries out the exchange second time again, condition is with for the first time, and washing then was 110～120 ℃ of dryings 6 hours.Dried beta-molecular sieve is at 550 ℃, constant temperature 10 hours.The beta-molecular sieve that ammonium is taken off in high-temperature roasting adds 1.2M HCl 4000ml through pulverizing weighing 400g, stirs and is warming up to 85 ℃, and constant temperature stirred 2 hours, filter, washing, in 110 ℃ of dryings 6 hours (butt＞80%).Above-mentioned exsiccant sample is carried out hydrothermal treatment consists, and temperature is 600 ℃, control pressure 0.3MPa, and the treatment time is 2 hours.
Embodiment 2
With 252.8 gram amorphous aluminum silicide (SiO
2Content be 65w%, pore volume is 0.58ml/g, specific surface area is 340m
2/ g), 9.4 the gram modifications beta-molecular sieves, 41.1 the gram macroporous aluminium oxides (pore volume is 0.75ml/g, and specific surface area is 360m
2/ g) put into the rolling machine mixed grind 20 minutes, (containing pore volume is that 0.45ml/g, specific surface area are 300m to add 323.1 gram tackiness agents then
2The aperture aluminum oxide 120.0g of/g, HPO
3With alumina molar ratio be 0.2), continued to roll 40 minutes, add 55 ml waters afterwards, roll to can squeezing paste, extrusion is extruded bar 140 ℃ of dryings 3 hours.Dried strip temperature programming to 530 ℃ roasting 5 hours gets carrier.Carrier is with the steeping fluid room temperature dipping of tungstenic, nickel 4 hours, 130 ℃ of dryings 3 hours, temperature programming to 460 ℃ roasting 5 hours, catalyst B.Physico-chemical property sees Table 1.
Wherein the beta-molecular sieve character of modification is: molecular sieve SiO
2/ Al
2O
3Weight ratio 60, specific surface 600m
2/ g, relative crystallinity are 105, infrared acidity 0.35mmol/g, and the secondary pore pore volume of 2～10nm accounts for 38% of total pore volume, average crystal grain diameter 0.3 μ m.Concrete modifying process is as follows: get industrial synthetic SiO
2/ Al
2O
3Weight ratio 25, Na
2The Na beta-molecular sieve slurries 2000ml of O 3.65w%, contain solid phase 400g (in butt), with water purification solid-to-liquid ratio is diluted to 1: 10, preparation 2.0M ammonium nitrate solution stirred, is warming up to 90 ℃ and constant temperature 3 hours, was cooled to 50 ℃ of filtrations, wet cake carries out second and third time exchange again, condition is with for the first time, and washing then was 110～120 ℃ of dryings 6 hours.Dried beta-molecular sieve is at 500 ℃, constant temperature 12 hours.The beta-molecular sieve that ammonium is taken off in high-temperature roasting adds 0.8M HCl 4000ml through pulverizing weighing 400g, stirs and is warming up to 90 ℃, and constant temperature stirred 4 hours, filter, washing, in 110 ℃ of dryings 6 hours (butt＞80%).Above-mentioned exsiccant sample is carried out hydrothermal treatment consists, and temperature is 570 ℃, control pressure 0.1MPa, and the treatment time is 3 hours.
Embodiment 3
With 201.4 gram amorphous aluminum silicide (SiO
2Content be 30w%, pore volume is 0.89ml/g, specific surface area is 460m
2/ g), 31.3 the gram modifications beta-molecular sieves, 82.8 the gram macroporous aluminium oxides (with embodiment 1) put into the rolling machine mixed grind 40 minutes, add 265.4 gram tackiness agents (with embodiment 1) then, continued to roll 25 minutes, add 30 ml waters afterwards, roll to squeezing paste, extrusion is extruded bar 130 ℃ of dryings 4 hours.Dried strip temperature programming to 680 ℃ roasting 2.5 hours gets carrier.Carrier is with the steeping fluid room temperature dipping of tungstenic, nickel 8 hours, 130 ℃ of dryings 4 hours, 530 ℃ of roastings 3 hours, catalyzer C.Physico-chemical property sees Table 1.
Wherein the beta-molecular sieve character of modification is: molecular sieve SiO
2/ Al
2O
3Weight ratio 85, specific surface 530m
2/ g, relative crystallinity are 100, infrared acidity 0.15mmol/g, and the secondary pore pore volume of 2～10nm accounts for 52% of total pore volume, average crystal grain diameter 0.2 μ m.Concrete modifying process is as follows: get industrial synthetic SiO
2/ Al
2O
3Weight ratio 25, Na
2The Na beta-molecular sieve slurries 2000ml of O 3.65w%, contain solid phase 400g (in butt), with water purification solid-to-liquid ratio is diluted to 1: 10, preparation 3.5M ammonium nitrate solution stirred, is warming up to 90 ℃ and constant temperature 2 hours, was cooled to 50 ℃ of filtrations, wet cake carries out the exchange second time again, condition is with for the first time, and washing then was 110～120 ℃ of dryings 6 hours.Dried beta-molecular sieve is at 600 ℃, constant temperature 10 hours.The beta-molecular sieve that ammonium is taken off in high-temperature roasting adds 2.5M HCl 4000ml through pulverizing weighing 400g, stirs and is warming up to 90 ℃, and constant temperature stirred 3 hours, filter, washing, in 110 ℃ of dryings 6 hours (butt＞80%).Above-mentioned exsiccant sample is carried out hydrothermal treatment consists, and temperature is 650 ℃, control pressure 0.4MPa, and the treatment time is 4 hours.
Embodiment 4
Present embodiment has been introduced catalyzer of the present invention carries out the hydro-upgrading isomerization-visbreaking to poor ignition quality fuel evaluation result.Processing condition see Table 4, the results are shown in Table 5.As can be seen from Table 5, adopt technology of the present invention can comprehensively improve the many index of diesel oil.Not only diesel product yield height, condensation point reduce that amplitude is big, cetane value improves significantly, and indexs such as diesel oil density, sulphur content, nitrogen content, T95 also be improved significantly.
The physico-chemical property of table 1. catalyzer
| Catalyzer | ????A | ????B | ????C |
| Carrier is formed and the character amorphous aluminum silicide, the w% modified beta molecular sieve, the w% macroporous aluminium oxide, the w% tackiness agent, w% pore volume/ml.g -1Specific surface area/m 2.g -1Catalyzer is formed and character WO 3，w％ NiO，w％ SiO 2，w％ Al 2O 3, w% pore volume/ml.g -1Specific surface area/m 2.g -1 | 53 6 16 25 0.596 300 20.3 5.1 22.2 surpluses 0.401 201 | 59 1 10 28 0.573 280 22.1 5.8 27.6 surpluses 0.372 182 | 47 10 20 23 0.618 336 25.2 6.6 16.3 surpluses 0.379 206 |
Table 2. stock oil character
| Stock oil | Straight-run diesel oil | Catalytic diesel oil | Coker gas oil | Medium diesel oil 1 | Medium diesel oil 2 |
| Density (20 ℃)/kgm -3T95/ ℃ of condensation point ℃ sulphur/μ gg -1Nitrogen/μ gg -1Paraffinic hydrocarbons, w% naphthenic hydrocarbon, w% aromatic hydrocarbons, the above aromatic hydrocarbons of w% two rings, the w% cetane value | ????824.4 ????381 ????+29 ????1400 ????207 ????60.5 ????26.9 ????12.6 ????6.1 | ????884.1 ????350 ????-4 ????2700 ????1378 ????30.3 ????14.2 ????55.5 ????35.9 ????27.1 | ????818.5 ????340 ????-2 ????846 ????1102 ????45.8 ????32.9 ????21.3 ????8.5 ????59.2 | ???860.4 ???370 ???+16 ???2200 ???992 ???45.3 ???17.1 ???37.6 ???24.2 ???47.6 | ???864.7 ???384 ???+5 ???1200 ???811 ???31.2 ???33.5 ???35.3 ???22.5 ???45.2 |
The main composition and the character of table 3.FH-98,3996 Hydrobon catalysts
| Catalyzer | ????FH-98 | ????3996 |
| The carrier reactive metal is formed, w% WO 3MoO 3NiO auxiliary agent P 2O 5, wt% auxiliary agent SiO 2, wt% pore volume/mlg -1Specific surface area/m 2·g -1 | ????γ-Al 2O 3??? ????20.2 ????9.3 ????4.2 ????3.7 ????/ ????0.30 ????140 | ????γ-Al 2O 3??? ????/ ????24.5 ????4.5 ????3.0 ????3.0 ????0.38 ????165 |
Table 4. embodiment 4 processing condition
| Test number | ????1 | ????2 | ????3 | 4 | 5 |
| Feedstock oil reaction formation catalyst agent volume ratio reaction temperature/℃ reaction pressure/MPa volume of hydrogen oil ratio cumulative volume air speed/h-1 | 2: 1 382/386 7.0/7.0 3,50/,350 1.09 of straight-run diesel oil series connection 3996/C | 1: 2 375/379 7.0/7.0 4,00/,400 1.09 of catalytic diesel oil series connection FH-98/A | 1: 2: 1 385/389 6.4/6.4 4,00/,400 1.50 of coker gas oil series connection 3996/B/A | Mixed diesel 1 single hop B/C 3: 1 379 8.0 800 1.94 | Mixed diesel 2 single hop A--403 12.0 1,000 3.01 |
Table 5. embodiment 4 test-results
| Test number | ????1 | ????2 | ????3 | ????4 | ????5 |
| Naphtha yield, w% petroleum naphtha virtue is dived, the w% diesel product yield, w% diesel product main character density (20 ℃)/kgm -3T95/ ℃ of condensation point/℃ sulphur/μ gg -1Nitrogen/μ gg -1Paraffinic hydrocarbons, w% naphthenic hydrocarbon, w% aromatic hydrocarbons, the above aromatic hydrocarbons of w% two rings, the w% cetane value | ????9.0 ????/ ????90.5 ?? ????805.8 ????360 ????-3 ????＜10 ????1.0 ????74.8 ????17.2 ????8.0 ????1.9 ????64.4 | ????2.0 ????56 ????98.0 ?? ????851.3 ????334 ????-18 ????＜10 ????1.0 ????42.5 ????12.1 ????45.4 ????12.6 ????40.3 | ????0.5 ????48 ????99.5 ?? ????790.0 ????313 ????-26 ????＜10 ????1.0 ????67.1 ????32.1 ????0.8 ????0.2 ????66.9 | ????3.9 ????52 ????96.1 ?? ????826.7 ????352 ????-10 ????＜10 ????1.0 ????62.5 ????23.7 ????13.8 ????1.3 ????55.8 | ????11.8 ????54 ????88.2 ?? ????828.8 ????348 ????-19 ????＜10 ????1.0 ????64.6 ????23.3 ????12.1 ????1.0 ????54.3 |
Claims (16)
1, a kind of hydro-upgrading isomerization-visbreaking is produced the method for diesel oil, with the distillate is raw material, adopt single hop or series process flow, under optimum conditions, distillate feedstock and hydrogen is by beds, obtains cleaning fine-quality diesel oil product and a small amount of sulphur nitrogen content is low, arene underwater content is high naphtha product; It is characterized in that described beds comprises a hydrotreating catalyst bed that contains beta-molecular sieve at least, hydrotreating catalyst comprises beta-molecular sieve, refractory porous oxide, group vib and the VIII family metal oxide of amorphous aluminum silicide, modification, weight percent with catalyzer is a benchmark, contain modified beta molecular sieve 1w%～9w% in the catalyzer, the silicon-dioxide of modified beta molecular sieve/aluminium sesquioxide weight ratio is 50～90, average grain size is 0.1～0.5 micron, infrared acidity 0.1～0.4mmol/g.
2, in accordance with the method for claim 1, it is characterized in that the described beta-molecular sieve hydrotreating catalyst that contains contains amorphous aluminum silicide 29w%～52w%, contain group vib metal 15w%～30w% in oxide compound, contain group VIII metal 3w%～9w% in oxide compound, porous refractory oxide 0w%～45w%, specific surface area of catalyst is 160～230m
2/ g, pore volume are 0.32～0.45ml/g.
3, in accordance with the method for claim 1, it is characterized in that described amorphous aluminum silicide content is 32w%～47w%, modified beta molecular sieve content is 2w%～8w%, the group vib metal is 18w%～26w% in oxide compound content, the group VIII metal is 5w%～7w% in oxide compound content, the porous refractory oxide is selected from one or more in aluminum oxide, titanium oxide, zirconium white, boron oxide and the above-mentioned elements compounding oxide compound, and porous refractory oxide content is 20w%～35w%.
4, in accordance with the method for claim 1, it is characterized in that the silicon-dioxide/aluminium sesquioxide weight ratio of described modified beta molecular sieve is 60～80, average grain size is 0.1～0.3 micron, and infrared acidity is 0.2～0.3mmol/g.
5, according to claim 1 or 4 described methods, the degree of crystallinity that it is characterized in that described modified beta molecular sieve is 90～110, and specific surface area is 400～750m
2/ g, pore volume are 0.25～0.50ml/g, Na
2O content is less than 0.10w%, and the secondary pore pore volume of 2～10nm accounts for 30～60% of total pore volume.
6, in accordance with the method for claim 5, the degree of crystallinity that it is characterized in that described modified beta molecular sieve is 100～110, and specific surface area is 500～600m
2/ g, pore volume are 0.3～0.4ml/g, Na
2O content is less than 0.05w%.
7, in accordance with the method for claim 1, it is characterized in that SiO in the described amorphous aluminum silicide
2Content be 20w%～75w%, pore volume is 0.5～1.1ml/g, specific surface area is 200～500m
2/ g; Described group vib metal is W and/or Mo, and the group VIII metal is Ni and/or Co.
8, in accordance with the method for claim 1, the preparation process that it is characterized in that the modified beta molecular sieve that described catalyzer contains comprises:
(1) the beta-molecular sieve slurries after the crystallization directly carry out ammonium exchange, filtration, washing, drying and roasting;
(2) beta-molecular sieve that takes off behind the ammonium of roasting carries out acid treatment;
(3) the intact beta-molecular sieve of acid treatment carries out hydrothermal treatment consists again.
9, in accordance with the method for claim 8, it is characterized in that the described ammonium exchange of step (1) is that the beta-molecular sieve slurries after the crystallization are directly carried out the ammonium salt exchange, the concentration of ammonium salt in slurries is 0.5～5.0mol/l, and several is carried out in the ammonium exchange, makes Na in the molecular sieve of exchange back
2The O weight content is not more than 0.5%; The described maturing temperature of step (1) is controlled at 450 ℃～650 ℃, and the time is 5.0～15.0 hours; The described acid treatment condition of step (2) is for being that the mineral acid of 0.1～5.0mol/l is carrying out acid treatment with concentration under abundant agitation condition, 20 ℃～100 ℃ of treatment temps, and the treatment time is 0.5～5.0 hour; The described hydrothermal treatment consists condition of step (3) for 100% water vapor at 500 ℃～800 ℃, be preferably 550 ℃～700 ℃, system pressure is 0.05～1.0MPa, handles 0.5～5.0 hour.
10, in accordance with the method for claim 1, it is characterized in that described distillate feedstock contains straight(-run) diesel distillate and/or secondary processing diesel oil cut.
11, in accordance with the method for claim 10, it is characterized in that described distillate feedstock is straight-run diesel oil, straight run light wax oil, catalytic diesel oil, coker gas oil, hydrotreatment diesel oil and above-mentioned one or more mixing oil.
12, in accordance with the method for claim 1, it is characterized in that described single hop hydroprocessing technique is to use a kind of type catalyst; Described series process flow refers to use dissimilar catalyzer to form the two or several different reaction zone of order, the dissimilar catalyzer of filling in a reactor, form the cascade reaction district, or use and use dissimilar catalyzer in two or more tandem reactors, form the cascade reaction district.
13,, it is characterized in that in the described serial hydrogenation treatment process that raw material is at first by conventional Hydrobon catalyst bed, then by containing the hydrotreating catalyst bed of beta-molecular sieve according to claim 1 or 12 described methods; The single hop hydroprocessing technique uses the hydrotreating catalyst that contains beta-molecular sieve.
14, in accordance with the method for claim 1, it is characterized in that described contain that beta-molecular sieve hydrotreating catalyst bed uses the character homogeneous contain the beta-molecular sieve hydrotreating catalyst, or use several different in kinds contain the beta-molecular sieve hydrotreating catalyst.
15, in accordance with the method for claim 1, it is characterized in that the reaction conditions of described distillate feedstock when containing the hydrotreating catalyst bed of beta-molecular sieve is reaction pressure 5.0～18.0MPa, hydrogen to oil volume ratio 500～1500, volume space velocity 0.5～4.0h
-1, 300～420 ℃ of temperature of reaction.
16, in accordance with the method for claim 13, it is characterized in that in the described serial hydrogenation treatment process, raw material is reaction pressure 0.5～18.0MPa by the operational condition of conventional Hydrobon catalyst bed at first, temperature 230～430, hydrogen to oil volume ratio 200～1500, volume space velocity 0.5～10.0h
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