CN101089137B - Mild hydrocracking process - Google Patents
Mild hydrocracking process Download PDFInfo
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- CN101089137B CN101089137B CN2006100469274A CN200610046927A CN101089137B CN 101089137 B CN101089137 B CN 101089137B CN 2006100469274 A CN2006100469274 A CN 2006100469274A CN 200610046927 A CN200610046927 A CN 200610046927A CN 101089137 B CN101089137 B CN 101089137B
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- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 57
- 230000008569 process Effects 0.000 title abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 84
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 239000002131 composite material Substances 0.000 claims abstract description 27
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 24
- 239000002283 diesel fuel Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 11
- 229910052721 tungsten Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 239000003245 coal Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 238000004523 catalytic cracking Methods 0.000 claims description 4
- 238000005987 sulfurization reaction Methods 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000004230 steam cracking Methods 0.000 claims description 3
- 239000011280 coal tar Substances 0.000 claims description 2
- 238000004939 coking Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 19
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000470 constituent Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 49
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 25
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
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- 238000005336 cracking Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 229910003296 Ni-Mo Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 241000219793 Trifolium Species 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
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- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
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- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
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- 239000007787 solid Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
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- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
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- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229940095054 ammoniac Drugs 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
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- VYQMZUUUGRXQHR-UHFFFAOYSA-N magnesium;oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Mg+2].[Ti+4] VYQMZUUUGRXQHR-UHFFFAOYSA-N 0.000 description 1
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- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
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Abstract
Hair brushIt relates to a mild hydrocracking process. The inferior diesel oil fraction, VGO and/or other heavy distillate oil are used as raw oil, and various products, especially hydrocracking tail oil with good properties, are obtained under mild hydrocracking operation conditions by adopting a single-stage or one-stage series process flow. Wherein the hydrogenation pretreatment reaction zone at least uses one bulk phase catalyst which is a composite oxide NixWyOzAnd oxide MoO3In a weight ratio of 1: 10-10: 1 constituent, composite oxide NixWyOzAnd oxide MoO3Accounting for 40 to 100 percent of the total weight of the catalyst composition. Compared with the prior art, the method can effectively reduce the operation severity of the hydrogenation pretreatment reaction zone, improve the treatment capacity of the device or prolong the service life of the catalyst and improve the product quality.
Description
Technical field
The present invention relates to a kind of mild hydrocracking method, particularly relate to a kind of strong catalyzer of hydrogenation performance that uses, with the mild hydrocracking method of inferior feedstock oil production cleaning light-end products and high-quality tail oil.
Background technology
Along with the increasingly stringent of environmental regulation, more and more higher to the specification of quality of automotive fuel.In the urban atmospheric pollution source, motor-vehicle tail-gas is an important component part.Therefore, more strict for the specification of quality of urban automobile automotive fuel.The automotive fuel overwhelming majority is by obtaining in the oil, oil obtains product through behind the multiple processing means, in these processing means, hydrocracking process is the most direct, the most effective method of producing high-quality product from poor heavy raw material oil, therefore hydrocracking technology has obtained attention in worldwide, and development has rapidly been arranged.
The characteristics that the hydrocracking process technology is the most outstanding are can direct production not have cleaning automotive fuels such as the clean diesel of sulphur, low aromatic hydrocarbons, high hexadecane value, high-quality rocket engine fuel, and high-quality petrochemical materialss such as light naphthar, heavy naphtha, tail oil.But also it is big to have a production handiness, characteristics such as liquid product yield height.General hydrocracking process is all selected for use than the operation down of higher pressure, has increased investment cost and process cost like this.And the hydroeracking unit of under the middle pressure condition, operating, it is relatively poor that the quality of light-end products compares, and especially tail oil character is poor.Hydrocracking generally comprises pre-treatment, filling hydrocracking pretreatment catalyst in the pretreatment reaction district, and generally the catalyzer of Cai Yonging is a conventional catalyst, because hydrocracking raw material oil becomes heavy variation day by day, and activity of such catalysts more and more can not meet the demands.Mild hydrocracking technology is a kind of in the hydrocracking technology, refers to operating under the demulcent condition relatively, and the cracking rate of raw material is lower, is purpose to obtain a large amount of tail oils and part light-end products.Because reaction depth is not high, its quality product remains further to be improved.
US4880526 discloses a kind of Ni of containing, Mo, W, the Co high reactivity is used for bulk phase catalyst of hydrotreatment and preparation method thereof, and this preparation method adopts metal to mix kneading to be equipped with technology, and the different metal component distributes under the microcosmic in mutually also inhomogeneous at body.US6299760, US6156695, US6537442, US6440888, the disclosed VIII of containing of US6652738 family/group vib active metal component are used for bulk phase catalyst of hydrotreatment and preparation method thereof, adopt and prepare the metal-powder that contains Ni-Mo or Ni-Mo-W earlier, use aluminum oxide bonding again, or the metal-powder of Ni-Mo or Ni-Mo-W is mixed back dehydration, extrusion, drying with alumina gel.Because the catalyst metal content height of this method preparation, often lack enough interactions between metal and aluminum oxide and cause catalyst strength poor.Active ingredient is made up of a large amount of metals, has some interior metal components and can not be fully utilized and cause the active ingredient loss in forming Ni-Mo or Ni-Mo-W powder process, and this problem can not be by simple bonding the solution.CN1342102A discloses a kind of mixed metal catalyst, and concrete grammar is for to obtain three kinds of reactive metal co-precipitation, and its main weak point is not find the cooperation effect between the different activities metal.US6162350, CN1339985A disclose a kind of mixed metal catalyst composition, and it is solid-state keeping at least a metal in preparation process, forms another kind of soild oxide in this solid metal compound surface reaction, finally forms the core-shell type composition.This method can not make different metal obtain good cooperation.
US4431517, US4683050 etc. have introduced mild hydrocracking method, and its hydrocracking pretreatment catalyst is conventional hydrogenation pretreatment catalyst.Patent disclosures such as CN1600840, CN1257106, CN1040046 a kind of mild hydrocracking method, the catalyzer that hydrogenation pretreatment reaction district uses in these patents all is conventional hydrocracking pretreatment catalysts.Owing to be subjected to the influence that stock oil becomes heavy variation day by day, use existing hydroeracking unit, operating severity increases, make the catalyzer life cycle shorten, be forced to reduce treatment capacity, perhaps new device need increase catalyst consumption, and because working pressure is low, hydrocracking tail oil generally can only provide charging for catalytic cracking.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of mild hydrocracking method, it can reduce the operating severity in hydrogenation pretreatment reaction district, promptly can be implemented under the lower pressure operation and obtain the reasonable various products of character, perhaps reduce temperature of reaction, increase the device processing power and prolong in the effect such as catalyzer work-ing life one or more.
The method of mild hydrocracking method of the present invention comprises following content: be raw material with the heavy distillate, under the hydrocracking operational condition, stock oil and hydrogen order are by hydrogenation pretreatment reaction district and hydrocracking reaction district, the hydrocracking that obtains generates oil and separates the gas circulation use that obtains in high-pressure separator, and the liquid that obtains is in the separation column fractionation.Described hydrogenation pretreatment reaction comprises a kind of bulk phase catalyst bed in the district at least, and bulk phase catalyst contains Mo, W, three kinds of metal components of Ni, and catalyzer W, Ni before sulfuration exist with the composite oxides form: Ni
xW
yO
z, z=x+3y, Mo exists with oxide form: MoO
3Composite oxides Ni
xW
yO
zThe ratio of middle x and y (atomic molar ratio) is 1:8～8:1, is preferably 1:4～4:1.Composite oxides Ni
xW
yO
zWith oxide M oO
3Weight ratio be 1:10～10:1, be preferably 1:5～5:1.Composite oxides Ni in the bulk phase catalyst
xW
yO
zWith oxide M oO
3Gross weight content be 40%～100%, be preferably 50%～80%.The productive rate of mild hydrocracking tail oil is more than the 30wt%, to be preferably 40wt%～85wt%, i.e. mild hydrocracking conversion of raw material is below the 70wt%, to be preferably 15wt%～60wt%.
The stock oil that the inventive method is used can be one or more in poor ignition quality fuel, VGO and other heavy distillate, as being VGO, CGO, HGO, the HCO etc. that obtain in the oil, and the poor-quality diesel-oil by cut fraction that produces of catalytic cracking, coking, thermally splitting, viscosity breaking, and be coal tar, gelatin liquefaction wet goods, and above-mentioned one or more.Can obtain various products from separation column: one or more gas, light naphthar, heavy naphtha, boat coal, diesel oil and the tail oil etc., wherein hydrocracking tail oil can provide high quality raw material for preparing ethylene by steam cracking, also can provide high quality raw material for catalytic cracking.
The operational condition in hydrocracking pretreatment reaction district is generally reaction pressure 4.0～20.0MPa, and hydrogen to oil volume ratio is 300:1～2500:1, and volume space velocity is 0.1～6.0h
-1, 310 ℃～455 ℃ of temperature of reaction; Preferred operational condition is reaction pressure 5.0～14.0MPa, hydrogen to oil volume ratio 500:1～2000:1, volume space velocity 0.2～4.0h
-1, 320～435 ℃ of temperature of reaction.The operational condition in hydrocracking reaction district is generally reaction pressure 4.0～20.0MPa, and hydrogen to oil volume ratio is 400:1～3000:1, and volume space velocity is 0.1～5.0h
-1, 310～450 ℃ of temperature of reaction; Preferred operational condition is reaction pressure 5.0～14.0MPa, hydrogen to oil volume ratio 500:1～2500:1, volume space velocity 0.2～4.0h
-1, 325 ℃～440 ℃ of temperature of reaction.
The catalyzer in mild hydrocracking pretreatment reaction of the present invention district can all be a bulk phase catalyst, also can be the combination of conventional hydrocracking pretreatment catalyst and bulk phase catalyst.During combination loading, bulk phase catalyst can be seated in the top of reaction zone, also can be seated in the bottom of reaction zone, and perhaps two types catalyzer loads at interval, the volume ratio of bulk phase catalyst and conventional catalyst is 90:10～10:90, preferred 20:80～80:20.During combination loading, preferred feed by bulk phase catalyst bed of the present invention, helps bringing into play the catalyzer overall activity most then earlier by common hydrocracking pretreatment catalyst bed.Wherein conventional hydrocracking pretreatment catalyst can be various commercial catalysts, as Fushun Petrochemical Research Institute (FRIPP) develop 3936,3996, Hydrobon catalysts such as FF-16, FF-26, the HC-K of Uop Inc., HC-P, the TK-555 of Topsor company, TK-565 catalyzer, the KF-847 of AKZO company, KF-848 etc.
The catalyzer of hydrocracking zone of the present invention is conventional hydrocracking catalyst.The carrier of hydrocracking catalyst is aluminum oxide and molecular sieve, and molecular sieve content is generally 5wt%～80wt%, commercial hydrocracking catalyst such as FRIPP develop 3882,3903 etc., the KC2702 of AKZO company etc.
Can contain in the components such as aluminum oxide, silicon oxide, amorphous aluminum silicide, phosphorous oxides, titanium oxide, Zirconium oxide, molecular sieve one or more in the bulk phase catalyst of the present invention as required, the weight content of these components in catalyzer is 0～60%, is preferably 20%～50%.The specific surface area of bulk phase catalyst is 120～400m
2/ g, pore volume are 0.10～0.50ml/g.
The preparation process of bulk phase catalyst of the present invention comprises following content: (1) coprecipitation method generates Ni
xW
yO
zThe composite oxides precursor; (2) Ni
xW
yO
zComposite oxides precursor and MoO
3Making beating mixes, filters; (3) moulding, activation are final catalyzer.
Wherein (1) described coprecipitation method generates Ni
xW
yO
zThe process of composite oxides precursor can adopt following method: with the salts solution of tungstenic, nickel, form required ratio in catalyzer and add in the glue jar, add precipitation agent and make gelatinous mixture.Precipitation agent can be inorganic or organic alkaline ammoniac compounds, is preferably ammonia, can working concentration ammoniacal liquor arbitrarily.
Add required catalyst adjuvant and add component in a step that can be in above-mentioned steps or a few step.Auxiliary agent generally comprise P, F, Ti, Si, B, Zr etc. one or more.Add component and be generally refractory porous mass and precursor thereof, as aluminum oxide and precursor (aluminium hydroxide, aluminum salt solution etc.), clay, sial, titanium oxide-magnesium oxide, molecular sieve etc.The method that adds auxiliary agent and interpolation component adopts this area ordinary method.
Though W, Mo, Ni are activity of hydrocatalyst component commonly used, find that through a large amount of The effects the performance of different fit system catalyzer has very big-difference.Particularly in the bigger bulk phase catalyst of total metal content, the different fit systems of these metals are bigger to the performance impact of catalyzer.The present invention finds by a large amount of experiments, is used for the body phase hydrogenation catalyst that the hydrocarbon material degree of depth is taken off impurity, earlier with W and Ni co-precipitation, makes Ni
xW
yO
zThe precursor of composite oxides, this composite oxides precursor again with MoO
3Making beating mixes, and adopts conventional means to prepare preformed catalyst then, and this preparation process organically cooperates element W and Ni, forms a kind of composite oxides, then with MoO
3Combination finally forms Ni
xW
yO
zThe composition of composite oxides and Mo oxide compound.The result shows when the catalyzer of this microtexture of the present invention is used for hydrocarbons hydrogenation, to have the outstanding impurity activity of taking off, and during especially for deep impurity removal process, significantly improves than the activity of such catalysts of similar chemical constitution.The mechanism that the composition of Ni-W composite oxides of the present invention and Mo oxide compound can improve catalyst activity is very not clear and definite as yet, and, in bulk phase catalyst, the content of reactive metal is higher, reactive metal exist form different fully with traditional loaded catalyst, therefore, can not be suitable for the metal cooperation theory of conventional negative supported catalyst.For example, it is generally acknowledged that Ni can promote the activity of Mo to improve, wishing has a stronger interaction between Ni and the Mo, and the present invention finds in experiment, for bulk phase catalyst, Mo and Ni is fully combined then take off impurity in the degree of depth and do not show perfect performance.The composition catalyzer of Ni-W composite oxides of the present invention and Mo oxide compound, the possible cause that takes off the unexpected raising of performance in the impurity in the degree of depth is, in the very high bulk phase catalyst of metal content, reactive metal exist form different with loaded catalyst, take off in the impurity process in the hydrocarbon raw material degree of depth, the Ni-W composite oxides have stronger hydrogenation activity after sulfuration, make to have the effective hydrogenation of complex construction hydrocarbon molecule, eliminate and take off the sterically hindered of impurity reaction.Has the stronger impurity activity of taking off after the Mo sulfuration in the bulk phase catalyst, simple in structure, the sterically hindered little heteroatoms hydrocarbon that contains is easy to react, reduced of the interference of this part heteroatoms hydro carbons, helped the hydrogenation that Ni-W high reactivity center is used for the complex construction molecule the Ni-W hydrogenation activity.After containing the effective hydrogenation in heteroatomic complex construction hydrocarbon molecule process Ni-W high reactivity center, take off the sterically hindered of impurity and reduce greatly, can in taking off impurity activity, remove easily in the heart.Therefore, the active centre of Ni-W composite oxides of the present invention and Mo oxide compound obtains cooperation, and combination catalyst takes off in the impurity reaction in the degree of depth and has outstanding activity.Bulk phase catalyst preparation method of the present invention does not use the salts solution of Mo, because the reaction product of Mo salts solution and precipitation agent generally has certain solubleness, has therefore avoided the loss of Mo.
Compared with prior art, characteristics of the present invention are: because the present invention has used some or all of highly active bulk phase catalyst, strengthened the hydrogenation performance of hydrocracking pretreatment reaction district catalyzer, can effectively reduce the content of organonitrogen in the stock oil, promptly under the identical operations condition, can reduce reaction pressure, reduce service temperature etc., perhaps under same reaction pressure, service temperature, increase the treatment capacity of device, perhaps reduce the usage quantity of catalyzer, thereby reduce the construction investment and the running cost of device.And, increased the aromatic hydrocarbons saturability greatly, thereby can increase substantially the quality of hydrocracking product, especially the quality of hydrocracking tail oil owing to improve the pretreated refining depth of hydrocracking.
Description of drawings
Fig. 1 is the principle process flow diagram (also claiming the single hop flow process) that the present invention adopts a reactor.
Fig. 2 is the principle process flow diagram (also claiming the one-stage serial flow process) that the present invention adopts two reactors.
Embodiment
Technical process of the present invention is single hop or one-stage serial hydrocracking technical process, adopts one way to pass through operating method.Those skilled in the art know, hydrocracking pretreatment reaction district and hydrocracking reaction district need the layering filling according to the temperature distribution situation, cold hydrogen inlet is arranged between each bed, inject cold hydrogen during operation, take away the reaction heat that hydrogenation reaction and cracking reaction produce, make temperature of reaction control within the specific limits, make operation safe, steady.
Mild hydrocracking method of the present invention is specific as follows: with one or more of poor ignition quality fuel, VGO and other heavy distillate is stock oil, adopt the one-stage serial technical process, under hydrocracking condition, stock oil and hydrogen order are by pretreatment reaction district and hydrocracking reaction district, the hydrocracking that obtains generates oil and separates the gas circulation use that obtains in high-pressure separator, and the liquid that obtains obtains various products in the separation column fractionation: gas, light naphthar, heavy naphtha, boat coal, diesel oil and tail oil etc.
Specifically technical process as shown in Figure 1: stock oil is mixed into all or part of high reactivity body of the filling hydrocracking pretreatment reaction district of hydrocracking pretreatment catalyst mutually with hydrogen, the hydrocracking pre-treatment that obtains generates oil and is mixed into the hydrocracking reaction district with hydrogen, the generation oil continuation fractionation separation column that obtains from the hydrocracking reaction district obtains gas, products such as light naphthar, heavy naphtha, boat coal, diesel oil, tail oil.
Bulk phase catalyst of the present invention can make as follows.
1, Ni
xW
yO
zComposite oxides precursor and MoO
3The preparation of mixture
In retort, add the saline solution that contains reactive metal Ni, W component by catalyst component content proportioning.Contain nickel salt and can be single nickel salt, nickelous nitrate, nickelous chloride etc.Tungstenic salt can be sodium wolframate, ammonium metawolframate etc.Mix the back, precipitation agent is added under stirring state in the said mixture, until forming collosol intermixture.Becoming the glue temperature is 30-100 ℃, and becoming the glue pH value is 7.0-10.0.Can become under the glue temperature to wear out 1-5 hour after becoming glue.Becoming in the glue thing promptly is Ni
xW
yO
zThe precursor of composite oxides.Can filter or not filter before and after becoming glue, add the solid molybdic oxide, making beating mixes, and filters then and obtains filter cake, and filter cake can wash or not wash, and filter cake dehydrates under 50-150 ℃ of condition, 0.5～24 hour time of drying, obtains Ni
xW
yO
zComposite oxides precursor and MoO
3Mixture.
Preferably 30～80 ℃ of described one-tenth glue temperature, gelation time was generally 0.5～5 hour, was preferably 0.5～3 hour, slurries pH value 7.0-9.0 preferably during cemented into bundles.Preferably 50～100 ℃ of described drying temperatures are preferably 1～8 hour time of drying.
Can add aluminum salt solution in the saline solution of Ni, W component, make the precursor that contains aluminum oxide in the throw out, aluminum salt solution can be aluminum nitrate, Tai-Ace S 150, aluminum chloride or aluminum acetate etc.Directly add aluminium hydroxide after also can becoming glue.The purpose of introducing aluminium in the catalyzer mainly is the intensity that increases catalyzer, and improves pore structure etc.In the preparation process of this mixture, can add auxiliary agent and additive etc. as required.
2, Preparation of Catalyst
The filter cake that above-mentioned drying is good rolls extruded moulding.Can or contain with water purification after the moulding and can decompose salt (as ammonium acetate) solution and wash.The activation of catalyzer comprises processes such as dry and roasting.To wash back stripe shape thing drying, roasting obtains final catalyst prod.Dry and roasting can be adopted this area normal condition, as 50～200 ℃ of dryings 1～48 hour, 450～600 ℃ of roastings 0.5～24 hour, is preferably 1～8 hour.Also can introduce auxiliary agent and additive as required in the catalyst preparation process.
Catalyst shape can be sheet, spherical, cylinder bar and special-shaped bar (trifolium, Herba Galii Bungei), preferably cylinder bar and special-shaped bar (trifolium, Herba Galii Bungei) as required.The diameter of carrier can be 0.8～2.0mm slice and the thick bar of 2.5mm.
Catalyzer has higher hydrodenitrification, hydrogenating desulfurization, the saturated isoreactivity energy of aromatic hydrocarbons.
Further specify Preparation of catalysts method of the present invention and use properties below by embodiment.The percentage composition that does not indicate benchmark is a weight percentage.
Embodiment 1
In retort, add 1000mL water, add nickelous chloride 40g dissolving then, add ammonium metawolframate 52g dissolving again, add zirconium oxychloride 5g dissolving again, add 10% ammoniacal liquor then and become glue, until pH value is 8, becoming the glue temperature is 50 ℃, wears out 1 hour behind the one-tenth glue, filters then, filter cake adds 600ml water purification and 16g molybdic oxide and 32g aluminium hydroxide, making beating stirs, and filters, and filter cake was 80 ℃ of dryings 5 hours, extruded moulding then, with water purification washing 3 times, wet bar is 120 ℃ of dryings 5 hours, 500 ℃ of roastings 4 hours, obtain final catalyst A, composition and main character see Table 1.
Embodiment 2
Method according to embodiment 1, press the component concentration proportioning of catalyst B in the table 1, adding aluminum chloride, nickelous chloride, sodium wolframate in retort, add 16% ammoniacal liquor then and become glue, is 9 until pH value, becoming the glue temperature is 80 ℃, wore out 3 hours after becoming glue, filter then, filter cake washs 2 times with the 500mL water purification, add water purification and molybdic oxide, making beating stirs, and filters, and filter cake was 70 ℃ of dryings 7 hours, extruded moulding then, with water purification washing 2 times, wet bar is 100 ℃ of dryings 8 hours, 550 ℃ of roastings 3 hours, obtain final catalyst B, composition and main character see Table 1.
Embodiment 3
Method according to embodiment 1, press the component concentration proportioning of catalyzer C in the table 1, in retort, add nickelous nitrate, ammonium metawolframate, aluminium hydroxide, silicon sol, add 12% ammoniacal liquor then and become glue, until pH value is 10, and becoming the glue temperature is 60 ℃, wears out 2 hours behind the one-tenth glue, filter then, filter cake adds molybdic oxide, and making beating stirs, and filters, filter cake was 120 ℃ of dryings 1 hour, extruded moulding then, wet bar is 130 ℃ of dryings 3 hours, 600 ℃ of roastings 3 hours, obtain final catalyzer C, composition and main character see Table 1.
Embodiment 4
Method according to embodiment 1, press the component concentration proportioning of catalyzer D in the table 1, in retort, add 1000mL water, add nickelous chloride 48g dissolving then, add ammonium metawolframate 40g dissolving again, adding 10% ammoniacal liquor then and become glue, is 8 until pH value, and becoming the glue temperature is 40 ℃, wore out 3 hours after becoming glue, filter then, filter cake adds 600ml water purification and 28g molybdic oxide and 17g aluminium hydroxide, and making beating stirs, filter, filter cake is 80 ℃ of dryings 5 hours, and extruded moulding then is with water purification washing 3 times, wet bar was 120 ℃ of dryings 5 hours, 500 ℃ of roastings 4 hours, obtain final catalyzer D, composition and main character see Table 2.
Comparative example
Catalyzer according to embodiment 1 is formed, and presses the disclosed method for preparing catalyst of Chinese patent CN1342102A, preparation reference agent E.
In retort, add 1000mL water, add Ammonium Heptamolybdate 25g dissolving then, add ammonium metawolframate 52g dissolving again, add 25% ammoniacal liquor then and become glue, until pH value is 10.0, and being heated to temperature is 90 ℃, drips the solution that contains the 40g nickelous chloride simultaneously in retort.The suspension liquid that forms is continued to stir 90 ℃ of temperature 30 minutes.Filter then, the filter cake hot wash, 100 ℃ of dryings 5 hours add 32g aluminium hydroxide extruded moulding then, and wet bar 500 ℃ of roastings 4 hours, obtains final reference catalyst E 100 ℃ of dryings 8 hours, and composition and main character see Table 2.Prepare catalyzer by this kind method, the molybdic oxide yield can only reach 80%, and in order to guarantee metal content and proportioning in the catalyzer, Ammonium Heptamolybdate adds 20% when feeding intake.
The catalyzer and the character of the preparation of table 1 the inventive method
| The catalyzer numbering | A | B | C | D | E |
| NiO，wt％ | 18.1 | 17.1 | 12.5 | 22.1 | 17.9 |
| WO 3，wt％ | 42.3 | 21.3 | 28.4 | 32.2 | 41.8 |
| MoO 3，wt％ | 16.5 | 57.6 | 18.6 | 28.1 | 17.0 |
| A1 2O 3，wt％ | Surplus | Surplus | Surplus | Surplus | Surplus |
| Other, wt% | ZrO 2/2.0 | Do not have | SiO 2/4.0 | TiO 2/3.0 | Do not have |
| Specific surface/m 2·g -1 | 143 | 258 | 202 | 135 | 105 |
| Pore volume/mlg -1 | 0.216 | 0.40 | 0.258 | 0.12 | 0.132 |
| Intensity/Nmm -1 | 11.5 | 11.0 | 16.7 | 18.2 | 8.6 |
Embodiment 5
Stock oil character sees Table 2, catalyst property sees Table 3, and processing condition and test-results see Table 4.Oxidized catalyst is carried out conventional sulfidizing before use.As under the 10MPa condition, vulcanize with the diesel oil that contains dithiocarbonic anhydride 2.0wt%, 230 ℃ of constant temperature 8 hours, 360 ℃ of constant temperature 10 hours, volume space velocity was 1.0h during liquid
-1, hydrogen to oil volume ratio is 1000:1.
From table 4 test-results as can be seen, adopt technology of the present invention can effectively improve the activity of hydrogenation catalyst, can reduce working pressure, reduce service temperature, perhaps improve treatment capacity, also can reduce the usage quantity of catalyzer, saved facility investment and process cost.Owing to the more intense hydrogenation performance of hydrocracking pretreatment catalyst, in hydrodenitrification, make the aromatic hydrocarbons degree of depth saturated, thereby promoted the quality of quality, the especially hydrocracking tail oil of hydrocracking product relatively simultaneously.Hydrocracking tail oil is fine preparing ethylene by steam cracking raw material or catalytically cracked material.
Table 2 stock oil character
| The stock oil title | Grand celebration VGO | Iran VGO | VGO in the sand | Isolated island VGO |
| Density/gcm -3 | 0.8688 | 0.9027 | 0.9269 | 0.9138 |
| Boiling range/℃ | 310～529 | 335～542 | 345～539 | 350～560 |
| Sulphur content, wt% | 0.12 | 1.28 | 2.58 | 0.77 |
| Nitrogen content/μ gg -1 | 360 | 1475 | 796 | 2300 |
| The BMCI value | 27.9 | 46.6 | 51.8 | 44.6 |
The main composition and the character of table 3. hydrogenation catalyst
| Catalyzer | FF-16 | 3882 | 3903 |
| Reactive metal is formed, wt% | |||
| WO 3 | 21.5 | 21.6 | |
| MoO 3 | 24.5 | ||
| NiO | 3.7 | 6.1 | 5.4 |
| P | 1.2 | ||
| Carrier | Surplus | Surplus | Surplus |
| Shape | Trifolium | Cylinder | Cylinder |
| Pore volume/mlg -1 | 0.35 | >0.30 | >0.31 |
| Intensity/Nmm -1 | >14 | >20 | >15 |
| Specific surface area/m 2·g -1 | >160 | >300 | 280 |
Table 4 embodiment 5 processing condition and test-results
| Processing condition | Process program 1 | Reference scheme 1 | Process program 2 | Reference scheme 2 |
| Catalyzer | A/3882 | FF-16/3882 | B/3903 | E/3903 |
| Stock oil | Iran VGO | Iran VGO | Grand celebration VGO | Grand celebration VGO |
| The catalyst loading volume ratio | 60:40 | 60:40 | 50:50 | 50:50 |
| Pressure/MPa | 10.0 | 10.0 | 6.0 | 6.0 |
| Hydrogen to oil volume ratio (pre-treatment/cracking) | 800:1/1200:1 | 800:1/1200:1 | 700:1/1100:1 | 700:1/1100:1 |
| Air speed/h -1 | 0.8/1.2 | 0.8/1.2 | 2.0/2.0 | 2.0/2.0 |
| Temperature/℃ | 376/372 | 385/374 | 375/385 | 380/387 |
| Treated oil nitrogen content/μ gg -1 | 15.9 | 29.2 | 14.3 | 20.6 |
| The heavy naphtha yield, wt% | 11.2 | 12.9 | 15.5 | 17.2 |
| The heavy naphtha virtue is dived | 56.4 | 50.1 | 42.6 | 40.5 |
| The boat yield of coal, wt% | 20.2 | 19.1 | 26.0 | 26.0 |
| Boat coal smoke point/mm | 25 | 19 | 23 | 21 |
| Naphthalene is a hydrocarbon, v% | — | — | 0.06 | 0.31 |
| Diesel yield, wt% | 15.1 | 14.6 | 10.7 | 11.9 |
| Diesel cetane-number | 51.5 | 42.4 | 56.4 | 50.8 |
| The tail oil yield, wt% | 50.1 | 50.0 | 45.2 | 45.5 |
| Tail oil sulphur content/μ gg -1 | 6.8 | 46.4 | 4.5 | 8.7 |
| Tail oil BMCI value | 13.9 | 26.5 | 10.7 | 13.6 |
Continuous table 4 embodiment 5 processing condition and test-results
| Processing condition | Process program 3 | Process program 4 |
| Stock oil | VGO in the sand | Isolated island VGO |
| Catalyzer | FF-16/C/3882 | D/3903 |
| The catalyst loading volume ratio | 30:30:40 | 40:60 |
| Pressure/MPa | 11.5 | 6.5 |
| Temperature/℃ | 373/373/384 | 386/378 |
| Processing condition | Process program 3 | Process program 4 |
| Air speed h/ -1 | 3.0/3.0/2.3 | 1.8/1.2 |
| Hydrogen to oil volume ratio (pre-treatment/cracking) | 900:1/900:1/1300:1 | 600:1/1000:1 |
| Treated oil nitrogen content/μ gg -1 | 16.9 | 30.3 |
| The heavy naphtha yield, wt% | 24.6 | 13.5 |
| The heavy naphtha virtue is dived | 56.2 | 53.5 |
| The boat yield of coal, wt% | 12.4 | 8.0 |
| Boat coal smoke point/mm | 25 | 23 |
| Naphthalene is a hydrocarbon, wt% | — | 0.14 |
| Diesel yield, wt% | 8.1 | 6.7 |
| Diesel cetane-number | 61.1 | 52.8 |
| The tail oil yield, wt% | 44.1 | 62.8 |
| Tail oil BMCI value | 11.2 | 18.7 |
Claims (8)
1. the method for a mild hydrocracking method, comprise following content: be stock oil with the heavy distillate, under the mild hydrocracking operational condition, stock oil and hydrogen order are by hydrogenation pretreatment reaction district and hydrocracking reaction district, the hydrocracking that obtains generates oil and separates the gas circulation use that obtains in high-pressure separator, the liquid that obtains enters separation column, and the mild hydrocracking conversion of raw material is 15wt%～60wt%; It is characterized in that comprising a kind of bulk phase catalyst bed at least in the described hydrogenation pretreatment reaction district, bulk phase catalyst contains Mo, W, three kinds of metal components of Ni, and catalyzer W, Ni before sulfuration exist with the composite oxides form: Ni
xW
yO
z, z=x+3y, Mo exists with oxide form: MoO
3, composite oxides Ni
xW
yO
zThe ratio of middle x and y is 1: 8～8: 1, composite oxides Ni
xW
yO
zWith oxide M oO
3Weight ratio be 1: 10～10: 1, composite oxides Ni in the bulk phase catalyst
xW
yO
zWith oxide M oO
3Gross weight content be 40%～100%; The operational condition in described hydrogenation pretreatment reaction district is: reaction pressure 4.0～20.0MPa, hydrogen to oil volume ratio are 300: 1～2500: 1, and volume space velocity is 0.1～6.0h
-1, 310 ℃～455 ℃ of temperature of reaction.
2. in accordance with the method for claim 1, it is characterized in that described bulk phase catalyst composite oxides Ni
xW
yO
zThe ratio of middle x and y is 1: 4～4: 1, composite oxides Ni
xW
yO
zWith oxide M oO
3Weight ratio be 1: 5～5: 1, composite oxides Ni in the bulk phase catalyst
xW
yO
zWith oxide M oO
3Gross weight content be 50%～80%.
3. in accordance with the method for claim 1, the operational condition that it is characterized in that the hydrocracking reaction district is reaction pressure 4.0～20.0MPa, and hydrogen to oil volume ratio is 400: 1～3000: 1, and volume space velocity is 0.1～5.0h
-1, 310～450 ℃ of temperature of reaction.
4. according to the described method of claim 1, it is characterized in that the operational condition in described hydrogenation pretreatment reaction district is: reaction pressure 5.0～14.0MPa, hydrogen to oil volume ratio 500: 1～2000: 1, volume space velocity 0.2～4.0h
-1, 320～435 ℃ of temperature of reaction; The operational condition in hydrocracking reaction district is reaction pressure 5.0～14.0MPa, hydrogen to oil volume ratio 500: 1～2500: 1, volume space velocity 0.2～4.0h
-1, 325 ℃～440 ℃ of temperature of reaction.
5. in accordance with the method for claim 1, the catalyzer that it is characterized in that described hydrocracking pretreatment reaction district all is a bulk phase catalyst, or the combination of conventional hydrocracking pretreatment catalyst and bulk phase catalyst; When being used in combination, the volume ratio of bulk phase catalyst and conventional catalyst is 90: 10～10: 90.
6. in accordance with the method for claim 5, the volume ratio that it is characterized in that described bulk phase catalyst and conventional catalyst is 20: 80～80: 20.
7. in accordance with the method for claim 1, it is characterized in that described stock oil is VGO, CGO, HGO, the HCO that obtains in the oil, in poor-quality diesel-oil by cut fraction that catalytic cracking, coking, thermally splitting, viscosity breaking produce and coal tar, the liquefied coal coil one or more.
8. in accordance with the method for claim 1, it is characterized in that to obtain tail oil as preparing ethylene by steam cracking raw material or catalytically cracked material from separation column.
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| CN103100423B (en) * | 2011-11-09 | 2014-12-31 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN103102962B (en) * | 2011-11-10 | 2015-02-18 | 中国石油化工股份有限公司 | Heating furnace rear-positioned poor quality gasoline distillate series connection hydrotreating method |
| CN103602347B (en) * | 2013-11-18 | 2016-01-20 | 中海石油舟山石化有限公司 | The method for hydrogen cracking of high-acid high-nitrogen low-sulfur naphthenic offshore oil |
| US10711207B2 (en) | 2014-10-22 | 2020-07-14 | Uop Llc | Integrated hydrotreating and slurry hydrocracking process |
| CN106590740B (en) * | 2015-10-15 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of inferior raw material oil treatment process |
| CN113549470B (en) * | 2020-04-24 | 2023-02-03 | 中国石油化工股份有限公司 | Catalytic cracking method |
| CN114717023B (en) * | 2021-01-06 | 2024-05-03 | 中国石油天然气股份有限公司 | Hydroconversion method |
| CN114713271B (en) * | 2021-01-06 | 2024-05-28 | 中国石油天然气股份有限公司 | Modified Y molecular sieve and preparation method thereof |
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| US4683050A (en) * | 1979-10-15 | 1987-07-28 | Union Oil Company Of California | Mild hydrocracking with a catalyst containing an intermediate pore molecular sieve |
| CN1600840A (en) * | 2003-09-28 | 2005-03-30 | 中国石油化工股份有限公司 | Method of mild hydrocracking raw material heavy oil |
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|---|---|---|---|---|
| US4683050A (en) * | 1979-10-15 | 1987-07-28 | Union Oil Company Of California | Mild hydrocracking with a catalyst containing an intermediate pore molecular sieve |
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