CN101165142A - Inferior distillate oil combination hydrogenation modified method - Google Patents
Inferior distillate oil combination hydrogenation modified method Download PDFInfo
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Abstract
The combined inferior distillate oil hydrogenating modification process includes hydrogenation modifying catalytically cracked diesel oil fraction material, hydrogenation refining pyrolytic distillate oil material, and separating the reaction effluent from both hydrogenation modifying and hydrogenation refining in a common separating system. The hydrogenating process of the present invention has high diesel oil yield, and is simple and low in cost, and the hydrogenated product has low content of S, P and other impurities and greatly raised cetane number. The process is suitable for hydrogenating of different types of inferior distillate oil material.
Description
Technical field
The present invention relates to a kind of integrated process for upgrading of inferior distillate oil, particularly improve the secondary processing distillate, especially inferior distillate oil hydrogenation associating modification combined methods such as catalytic cracking diesel oil, coker gas oil, coking gasoline and diesel.
Background technology
At present the trend that heaviness and poor qualityization accelerate has appearred in the world and domestic crude oil, the oil field scope that relates to also more and more widely, the increasingly stringent of the sustainable development of world economy and environmental regulation in addition, need to produce a large amount of light clean fuels, these all require existing oil Refining Technologies is improved, and produce satisfactory product with minimum cost.Because the poor qualityization of raw material, not only make the degradation of straight-run diesel oil, and the quality that comes from the secondary processing diesel oil cut of heavy oil lighting devices such as catalytic cracking and coking can be poorer, adopt existing technology to be difficult to the qualified diesel product that direct production conforms to quality requirements, this just requires to develop new working method.
Existing secondary processing distillate improves the quality of products and mainly finishes by hydrogenation process, comprising: hydrofining technology, middle pressure hydrocracking technology and hydro-upgrading technology.
The hydrofining technology mainly contains two kinds: a kind of is with the single hop hydrofining under middle pressure or low pressure of secondary processing diesel oil cut, as FR2764902, RU2058371, US5068025, US5543036, US5817594, US5035793 etc., diesel oil fraction hydrogenating purified technology is all disclosed, this technology can be easy to make the sulphur content in the cut to reach low-down level, but the cetane value increase rate is very little, basically at 3～6 units, and the aromatic hydrocarbons degree of saturation is poor.
Another kind is to use two sections purification techniquess of noble metal catalyst, it can guarantee that sulphur, nitrogen in the diesel oil remove fully with aromatic hydrocarbons and removes in a large number in second section in first section, make sulphur in the product, nitrogen and aromaticity content reach requirement, as US5556824 and US5651878 etc., but the one-time investment of its catalyzer and device is very huge, divide two sections operations again, operation is very complicated, and the stability of catalyzer awaits further to verify, because volume space velocity is smaller, the processing power of device is limited in addition.
Adopt the middle pressure hydrocracking technology, as US5611912, US4985134, US4971680 and US4483760 etc., although the index of diesel oil distillate has all satisfied the requirement of specification, but liquid yield is lower, outstanding tool is the purpose product---it is more that diesel yield reduces, and the gasoline fraction octane value that cracking obtains is low, also needs the reformation technology further to process, and the hydrogen consumption is also very big.
Adopt the diesel oil fraction hydrogenating modification technology, as CN1156752A and CN1289832A etc., although can increase substantially diesel-fuel cetane number and reduce foreign matter contents such as sulphur, nitrogen, this technology is only applicable to the diesel raw material that cetane value is low, aromaticity content is high.
In the refining of petroleum enterprise, catalytic cracking and coking are two kinds of most important, that amount of finish is maximum heavy oil lighting technological processs, the quality of the distillates such as diesel oil that two kinds of processes obtain all can not satisfy the quality product requirement, prior art adopts the hybrid process mode usually to the diesel oil distillate that two kinds of processes obtain, or with diesel raw material (as straight-run diesel oil etc.) the hybrid process mode in other source, though hybrid process has the simple advantage of technological process, is unfavorable for comprehensively improving the quality of products.
Summary of the invention
At the deficiencies in the prior art, the invention provides and a kind ofly carry out the combination hydrogenation modified technological process of upgrading targetedly at the different properties raw material, the diesel product cetane value height of gained, sulphur and nitrogen content are low, are the clean diesel products that meets environmental regulation and specification requirement.
It is wide that the diesel oil distillate that catalytic cracking process obtains has boiling range, aromaticity content height, characteristics such as cetane value is low.It is wide that the vapour that coking obtains, diesel oil distillate have boiling range, sulphur, nitrogen content height, characteristics such as aromaticity content is relatively low.The present invention is directed to the inferior distillate oil of different sources, determine following combination hydrogenation modified technological process, specifically comprise the steps:
A, under the hydro-upgrading operational condition, the catalytic cracking diesel oil cut is through the catalyst for hydro-upgrading bed;
B, under the hydrofining operational condition, coking distillate is through the Hydrobon catalyst bed;
C, step a and step b reaction effluent enter gas-liquid separator, comprise that the gas phase of hydrogen recycles behind depriving hydrogen sulphide, and liquid phase enters the fractionating system fractionation and obtains various hydrocarbon liquid phase series products.
The cetane value of the described catalytic cracking diesel oil raw material of step a is less than 35, and aromaticity content is greater than 45wt%, and preferred cetane value is that aromaticity content is greater than 50wt% less than 30.The described coking distillate of step b comprises coker gasoline and/or coker gas oil, the cetane value of coker gas oil 〉=35, aromaticity content≤45wt%, preferred cetane value is greater than 40, aromaticity content is less than 35wt%, the sulphur nitrogen content is higher, and sulphur content (by weight) is generally 1%～4%, and nitrogen content is generally 500～15000 μ g/g.Coking gasoline and diesel is from the coker gasoline of coker and the mixing oil of coker gas oil, and its boiling range is generally 64 ℃～380 ℃.
Catalytic diesel oil that step a uses can carry out fractionation earlier, and cut point is 190～235 ℃, and the lighting end of telling mixes with the coking distillate of step b carries out hydrofining, and the last running that fractionates out is carried out hydro-upgrading and handled.
The described catalyst for hydro-upgrading of step a is the catalyst for hydro-upgrading that contains Modified Zeolite Y, and catalyzer contains WO by weight
315%～30%, NiO or CoO2%～15%, Modified Zeolite Y 10%～45% can contain auxiliary agent such as F simultaneously, and F content is 1%～9% by weight, and carrier is aluminum oxide and/or amorphous aluminum silicide.Wherein Modified Zeolite Y has following character: lattice constant is 2.436～2.444nm, and infrared total acid (160 ℃) is 0.5～1.1mmol/g.
The described hydro-upgrading operational condition of step a is: stagnation pressure 4.0MPa～18.0MPa, temperature of reaction is 300 ℃～440 ℃, volume space velocity 0.3h during liquid
-1～4.0h
-1, hydrogen to oil volume ratio is 100: 1～2000: 1.
The described hydrofining of step b can be adopted the common Hydrobon catalyst in this area, also can adopt high-activity hydrofining catalyst, also can adopt common Hydrobon catalyst and high-activity hydrofining catalyst to be used by suitable way, 1: 5 by volume～5: 1 ratios of preferred common Hydrobon catalyst and high-activity hydrofining catalyst are used, material at first by common Hydrobon catalyst, passes through high-activity hydrofining catalyst then.Common Hydrobon catalyst can be selected the commercially available prod, and generally with aluminum oxide or to contain the auxiliary agent aluminum oxide be carrier, so that one or more are active metal component among W, Mo, Ni, the Co etc., active metal component is 15%～45% in the oxide weight total content.High-activity hydrofining catalyst is a kind of bulk phase catalyst, 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 described hydrofining operational condition of step b is generally: stagnation pressure 4.0MPa～18.0MPa, temperature of reaction is 260 ℃～440 ℃, volume space velocity 0.3h during liquid
-1～6.0h
-1, hydrogen to oil volume ratio is 100: 1～2000: 1.The hydrogenation process of step a and step b adopts same pressure rating, common gas-liquid separator easy to use and common recycle hydrogen compressor.
The present invention is by optimizing the inferior distillate oil raw material of different sources, adopt suitable technical process and optimize suitable catalyzer and operational condition, the inferior raw material of different sources is improved the quality of products under optimum, finally obtained ideal comprehensive process effect.In technical process, the inventive method and two kinds of raw materials add have saving equipment man-hour (gas-liquid separation equipment, stripping apparatus, compressor etc.), advantage such as technical process is short, facility investment is low, process cost is low respectively.The general boiling range broad of catalytic cracking diesel oil raw material, wherein may contain part kerosene even gasoline fraction, these relative light-weight cuts are in containing the catalyst for hydro-upgrading of molecular sieve, further cracking is small molecules even gas molecule, reduced particularly diesel product yield reduction of liquid yield, the more important thing is, dicyclo in the light ends, the light content of many cyclophanes is less, and dicyclo and polycyclic aromatic hydrocarbons are the suitable raw materials of hydro-upgrading raising product property (mainly being to improve the product cetane value), after non-suitable upgrading raw material is told, the upgrading degree of depth that helps deepening other raw material.The catalyzer that the upgrading of poor-quality diesel-oil by cut fraction need suit, the catalyzer that contains Modified Zeolite Y of optimized choice of the present invention has characteristics such as upgrading is deep, purpose product (diesel oil) yield height, is suitable for technological process of the present invention.Coking distillate has characteristics such as sulphur, nitrogen content height, and wherein the organism of sulfur-bearing, nitrogen impurity has different types, more promptly belongs to easily to remove impurity, and some belong to difficulty and remove impurity.These characteristics at coking distillate, design a kind of dissimilar hydrogenation catalyst and be used technology, guarantee all to have on the whole beds suitable hydrogenation and taken off the impurity reaction, bed temperature is evenly distributed (hydrogenation takes off the impurity reaction and is thermopositive reaction), quality product height, catalyzer long service life.
Description of drawings
Fig. 1 is one embodiment of the present invention schematic flow sheets.
Fig. 2 is the another embodiment of the invention schematic flow sheet.
Wherein: 1 is the catalytic cracking diesel oil raw material, 2 are hydro-upgrading hydrogen, and 3 is the hydro-upgrading reactor, and 4 are hydro-upgrading generation oil, 5 is the coking distillate raw material, 6 are hydrofining hydrogen, and 7 is hydrofining reactor, and 8 are hydrofining generation oil, 9 is gas-liquid separator, 10 is recycle hydrogen, and 11 is new hydrogen, and 12 is compressor, 13 is the reaction solution effluent, 14 is the product separation column, and 15 for fractionation obtains gas, and 16 obtain gasoline for fractionation, 17 obtain diesel oil for fractionation, 18 is catalytic cracking diesel oil raw material separation column, and 19 is the last running of catalytic cracking diesel oil raw material, and 20 is the lighting end of catalytic cracking diesel oil raw material.
Embodiment
The described hydro-upgrading of step a can basis the feedstock property difference, adjust accordingly, if raw material sulphur nitrogen impurity content is lower, can use catalyst for hydro-upgrading separately, if raw material sulphur nitrogen impurity is higher, can be before catalyst for hydro-upgrading, raw material contacts with Hydrobon catalyst earlier, removes impurity such as part sulphur nitrogen wherein.Hydrobon catalyst can be conventional Hydrobon catalyst, as the extensive stock Hydrobon catalyst.Catalyst for hydro-upgrading can root character require to select commercial catalyst for hydro-upgrading, also can need prepare corresponding Modified Zeolite Y by character, then by this area conventional catalyst preparation method such as immersion process for preparing.Wherein Modified Zeolite Y can prepare according to the following steps: industrial synthetic NaY molecular sieve exchanges with ammonium salt, obtains Na
2The O weight content is lower than 3% NH
4NaY, in slurries, carry out contact reacts then with ammonium hexafluorosilicate, temperature is 50～120 ℃, preferred 70～100 ℃, reaction times is 0.5～24 hour, and the consumption of ammonium hexafluorosilicate is 20%～50% of a molecular sieve weight, isolates product then, separated product obtains final Modified Zeolite Y in 450～650 ℃ and 0.05～0.2MPa (gauge pressure) hydrothermal treatment consists 1～4 hour down.
The described conventional Hydrobon catalyst of step b can be selected the commodity Hydrobon catalyst, FH-5, the FH-5A that produces as Fushun Petrochemical Research Institute's development tissue, FH-98, FH-DS, FH-UDS, 3936, Hydrobon catalysts such as 3996, the function class that also can be other catalyst Co. exploitation is like catalyzer, HC-K, HC-P as Uop Inc., KF-847, the KF-848 etc. of the TK-555 of Topsor company, TK-565 catalyzer and AKZO company.
The described high-activity hydrofining catalyst of step b can select to meet the commodity Hydrobon catalyst of performance requriements, preferably adopts specified high reactivity body phase Hydrobon catalyst among the application.The concrete preparation process of this catalyzer is as follows: 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 macromole, 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 macromole 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.
The present invention can adopt suitable technical process, catalyzer and processing condition according to the difference of feedstock property and product requirement.The percentage composition that relates among the present invention is a weight percentage.
Figure 1 shows that one embodiment of the present invention principle flow chart, at first catalytic cracking diesel oil raw material 1 is mixed into hydro-upgrading reactor 3 with hydrogen 2, obtains the low hydro-upgrading of impurity such as sulfur-bearing, nitrogen and generates oil 4.Coking distillate raw material 5, and hydrogen 6 be mixed into hydrofining reactor 7, through series reaction, obtain hydrofining and generate oil 8.Hydro-upgrading generates oil 4 and hydrofining generation oil 8 enters gas-liquid separator 9, being separated into high pressure hydrogen-rich gas 10 mixes after compressor 12 loops back hydro-upgrading reactor 3 and hydrofining reactor 7 with new hydrogen 11, the liquid product of separating 13 enters separation column 14, and further fractionation obtains gas 15, gasoline 16 and diesel oil 17.Fig. 2 is another kind of embodiment principle flow chart, when being applicable to the boiling range broad of catalytic cracking diesel oil raw material, difference is the catalytic cracking diesel oil raw material is separated into lighting end 20 and last running 19 in separation column 18, last running 19 enters hydro-upgrading reactor 3, lighting end 20 is mixed into hydrofining reactor 7 with coking distillate raw material 5, and other is identical with Fig. 1 flow process.Further specify characteristics of the present invention and effect below in conjunction with embodiment.
The common Hydrobon catalyst trade mark that relates to is FH-98, for Fushun Petrochemical Research Institute's development, is produced by Wenzhou catalyst plant.
The high-activity hydrofining catalyst HT preparation process that relates to is as follows.
High-activity hydrofining catalyst HT-A preparation:
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 catalyzer HT-A, composition and main character see Table 1.
High-activity hydrofining catalyst HT-B preparation:
According to HT-A Preparation of catalysts process, press the component concentration proportioning of catalyzer HT-B in the table 1, in retort, add aluminum chloride, nickelous chloride, sodium wolframate adds 16% ammoniacal liquor then and becomes 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 catalyzer HT-B, composition and main character see Table 1.
The composition of table 1 high-activity hydrofining catalyst and main character
| The catalyzer numbering | HT-A | HT-B |
| NiO，wt％ | 18.1 | 17.1 |
| WO 3，wt％ | 42.3 | 21.3 |
| MoO 3，wt％ | 16.5 | 57.6 |
| Al 2O 3，wt％ | Surplus | Surplus |
| Other, wt% | ZrO 2/2.0 | Do not have |
| Specific surface/m 2·g -1 | 143 | 258 |
| Pore volume/mlg -1 | 0.216 | 0.40 |
| Intensity/Nmm -1 | 11.5 | 11.0 |
The catalyst for hydro-upgrading HC preparation process that relates to is as follows:
Take by weighing the industrial NaY molecular sieve (SiO of 500 grams
2/ Al
2O
3=4.66, lattice constant 2.463) with 2M ammonium nitrate solution 1L 35 ℃ of exchanges 2 hours down, filter NH
4NaY molecular sieve (Na
2O 2.5w%), add 2.5 liters of distilled water, heat temperature raising to 95 ℃ under agitation condition, in 2 hours, drip 1.0M hexafluorosilicic acid aqueous ammonium 870ml with even velocity, add rear slurry and continue down to stir 2 hours at 95 ℃, filter out molecule then, hydrothermal treatment consists is 2 hours under 600 ℃ and 0.15MPa pressure, obtaining the molecular sieve lattice constant is 2.438nm, and infrared total acid is 0.65mmol/g.
With this modified molecular screen 200, add 75 gram amorphous silicon aluminiums, adding 115 gram crystalline phases again is aluminum oxide (pore volume 0.50ml/g, the specific surface area 210m of pseudo-boehmite
2/ g) become bonding agent with 190ml 0.2M nitric acid peptization, mixed rolling, extrusion, 120 ℃ of dryings 2 hours, 550 ℃ of roastings made support of the catalyst in 4 hours.Getting carrier 100 gram is 8% citric acid solution dipping 2 hours with 200ml concentration, filters, and filters bar and (contains WO with tungsten, the nickel steeping fluid of 200ml
356%, NiO 18%) dipping 2 hours, filter, 110 ℃ of dryings 4 hours, 500 ℃ of roastings 5 hours must be got catalyst for hydro-upgrading HC-1.Get the ammonium fluoride solution that HC-1 150 gram adds 300ml 4wt% and under room temperature, stirred 1 hour, 110 ℃ of dryings 4 hours, 500 ℃ of roastings 4 hours, fluorine content is 3.5% in the catalyzer, obtains catalyst for hydro-upgrading HC-2.
Use the main character of stock oil to see Table 2.
Table 2 stock oil character
| The stock oil title | Stock oil-1 | Stock oil-2 | Stock oil-3 | Stock oil-4 |
| The source | Catalytic cracking diesel oil | Catalytic cracking diesel oil | Coker gas oil | Coking gasoline and diesel |
| Density (20 ℃)/gcm -3 | 0.8813 | 0.9385 | 0.8750 | 0.8201 |
| The boiling range scope, ℃ | 180～361 | 167～372 | 178～365 | 64～357 |
| Sulphur content, wt% | 0.76 | 0.35 | 1.65 | 0.95 |
| Nitrogen content, wt% | 0.06 | 0.09 | 0.09 | 0.07 |
| Cetane value | 37.1 | 24.0 | 49.5 | |
| Aromaticity content, wt% | 41.2 | 70.4 | 29.5 | 15.9 |
Embodiment 5 presses Fig. 2 flow operations, with reference to embodiment 3 described conditions, is last running and lighting end with the catalytic cracking diesel oil raw material by 210 ℃ of fractionation, and hydro-upgrading is carried out in last running, and lighting end mixes with coking distillate carries out hydrofining.
Table 3 hydro-upgrading operational condition and result
| Numbering | |
|
|
|
Embodiment 5 |
| Stock oil | Stock oil-1 | Stock oil-1 | Stock oil-2 | Stock oil-2 | Stock oil-2 last running |
| Catalyzer | FH-98/ HC-1 | HC-2 | FH-98/ HC-1 | FH-98/ HC-2 | FH-98/ HC-1 |
| Catalyst ratio (v/v) | 40/60 | / | 50/50 | 20/80 | 50/50 |
| Reaction pressure/MPa | 8.0 | 6.0 | 10.0 | 12.0 | 10.0 |
| Average reaction temperature/℃ | 375 | 350 | 365 | 345 | 365 |
| LHSV/h -1 | 1.0 | 1.2 | 0.8 | 1.5 | 0.8 |
| Hydrogen to oil volume ratio (v/v) | 500∶1 | 700∶1 | 1300∶1 | 800∶1 | 1300∶1 |
| ＜145 ℃ of gasoline fractions | |||||
| Yield, wt% | 3.5 | 2.1 | 3.0 | 4.4 | 2.6 |
| Sulphur content/μ gg -1 | 25 | 30 | 15 | 3 | 16 |
| 〉=145 ℃ of diesel oil distillates | |||||
| Yield, wt% | 96.0 | 97.5 | 95.8 | 95.0 | 96.2 |
| Density (20 ℃)/gcm -3 | 0.8421 | 0.8446 | 0.8605 | 0.8495 | 0.8609 |
| Sulphur content/ |
20 | 30 | 18 | 8 | 19 |
| Cetane value | 49.8 | 47.5 | 40.1 | 45.6 | 42.1 |
| Aromatic hydrocarbons, wt% | 18.1 | 19.5 | 32.5 | 26.7 | 34.3 |
Table 4 hydrofining operational condition and result
| Numbering | |
|
|
|
Embodiment 5 |
| Stock oil | Stock oil-3 | Stock oil-4 | Stock oil-3 | Stock oil-4 | Stock oil-3+stock oil, 2 lighting ends |
| Catalyzer | FH-98/ HT-A | FH-98/ HT-B | FH-98 | FH-98/ HT-A | FH-98 |
| Catalyst ratio (v/v) | 70/30 | 40/60 | / | 50/50 | / |
| Reaction pressure/MPa | 8.0 | 6.0 | 10.0 | 12.0 | 10.0 |
| Temperature of reaction/℃ | 350 | 340 | 330 | 345 | 330 |
| LHSV/h -1 | 2.0 | 1.5 | 3.0 | 4.0 | 3.0 |
| Hydrogen to oil volume ratio (v/v) | 300∶1 | 600∶1 | 800∶1 | 400∶1 | 800∶1 |
| ＜145 ℃ of gasoline fractions | |||||
| Product yield, wt% | 1.3 | 14.5 | 0.9 | 16.8 | 0.8 |
| Sulphur content/μ gg -1 | 65 | 50 | 15 | ＜1 | 14 |
| 〉=145 ℃ of diesel oil distillates | 97.8 | 85.1 | 98.3 | 82.1 | 98.1 |
| Density (20 ℃)/gcm -3 | 0.8315 | 0.8341 | 0.8265 | 0.8204 | 0.8203 |
| Sulphur content/μ gg -1 | 110 | 80 | 50 | 5 | 35 |
| Cetane value | 52.1 | 51.9 | 53.3 | 54.6 | 53.0 |
| Aromatic hydrocarbons, wt% | 20.5 | 21.2 | 18.7 | 15.4 | 19.1 |
Table 5 embodiment products obtained therefrom character
| | Embodiment | 1 | |
|
|
Embodiment 5 |
| The diesel oil ratio, wt% upgrading diesel oil: refined diesel oil | 40∶60 | 50∶50 | 60∶40 | 50∶50 | 50∶50 | |
| Density (20 ℃)/gcm -3 | 0.8350 | 0.8401 | 0.8512 | 0.8360 | 0.8506 | |
| Sulphur content/μ gg -1 | 75 | 55 | 35 | 7 | 27 | |
| Cetane value | 51.4 | 50.1 | 44.5 | 50.1 | 47.5 | |
| Aromatic hydrocarbons, wt% | 19.4 | 20.3 | 26.4 | 21.3 | 26.7 |
From above embodiment, come as can be seen, the maximum characteristics of this combination process are, rationally utilize the characteristics separately of hydrogenation modifying process and hydrofining technology, when keeping higher diesel oil distillate yield, both reduce the content of impurity such as sulphur, nitrogen and aromatic hydrocarbons significantly, also increased substantially the cetane value of diesel product.Owing to adopted combination process, also reduced the facility investment and the process cost of device.From embodiment 5 as can be seen, with the processing scheme after the separation of the lighting end in the catalytic cracking diesel oil raw material, the finished product character can further improve.
Claims (13)
1. an inferior distillate oil combination hydrogenation modified method comprises catalytic cracking diesel oil feedstock and coking distillate raw material, comprises the steps:
A, under the hydro-upgrading operational condition, the catalytic cracking diesel oil cut is through the catalyst for hydro-upgrading bed, described catalyst for hydro-upgrading contains Modified Zeolite Y;
B, under the hydrofining operational condition, coking distillate is through the Hydrobon catalyst bed;
C, step a and step b reaction effluent enter gas-liquid separator, and gas phase recycles behind depriving hydrogen sulphide, and liquid phase enters the fractionating system fractionation and obtains various hydrocarbon productss.
2. in accordance with the method for claim 1, the cetane value that it is characterized in that the described catalytic cracking diesel oil raw material of step a is for less than 35, and aromaticity content is greater than 45wt%; The described coking distillate of step b comprises coker gasoline and/or coker gas oil.
3. in accordance with the method for claim 1, it is characterized in that step a uses the catalytic diesel oil raw material to carry out fractionation earlier, cut point is 190～235 ℃, and the lighting end of telling mixes with the coking distillate of step b carries out hydrofining, and the last running that fractionates out is carried out hydro-upgrading and handled.
4. in accordance with the method for claim 1, it is characterized in that the described catalyst for hydro-upgrading of step a is the catalyst for hydro-upgrading that contains Modified Zeolite Y, Modified Zeolite Y has following character: lattice constant is 2.436～2.444nm, and infrared total acid is 0.5～1.1mmol/g.
5. according to claim 1 or 4 described methods, it is characterized in that described catalyst for hydro-upgrading by weight catalyzer contain WO
315%～30%, NiO or CoO 2%～15%, Modified Zeolite Y 2%～45%, carrier is aluminum oxide and/or amorphous aluminum silicide.
6. according to claim 1 or 4 described methods, it is characterized in that described catalyst for hydro-upgrading contains auxiliary agent F, F content is 1%～9% by weight.
7. in accordance with the method for claim 1, it is characterized in that the described hydro-upgrading operational condition of step a is: stagnation pressure 4.0MPa～18.0MPa, temperature of reaction is 300 ℃～440 ℃, volume space velocity 0.3h during liquid
-1～4.0h
-1, hydrogen to oil volume ratio is 100: 1～2000: 1.
8. in accordance with the method for claim 1, it is characterized in that the described hydrofining of step b adopts common Hydrobon catalyst and high-activity hydrofining catalyst to be used by suitable way, common Hydrobon catalyst and high-activity hydrofining catalyst 1: 5 by volume～5: 1, material at first by common Hydrobon catalyst, passes through high-activity hydrofining catalyst then.
9. in accordance with the method for claim 8, it is characterized in that described common Hydrobon catalyst is with aluminum oxide or to contain the auxiliary agent aluminum oxide be carrier, so that one or more are active metal component among W, Mo, Ni, the Co, active metal component is 15%～45% in the oxide weight total content.
10. in accordance with the method for claim 8, it is characterized in that described high-activity hydrofining catalyst is a kind of bulk phase catalyst, 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 atomic molar 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%.
11. in accordance with the method for claim 10, it is characterized in that composite oxides Ni in the described bulk phase catalyst
xW
yO
zThe atomic molar 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%.
12. in accordance with the method for claim 1, it is characterized in that the described hydrofining operational condition of step b is: stagnation pressure 4.0MPa～18.0MPa, temperature of reaction is 260 ℃～440 ℃, volume space velocity 0.3h during liquid
-1～6.0h
-1, hydrogen to oil volume ratio is 100: 1～2000: 1.
Adopt same pressure rating 13. it is characterized in that in accordance with the method for claim 1, the hydrogenation process of step a and step b.
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