CN100569921C - A kind of single-stage hydrocracking process - Google Patents
A kind of single-stage hydrocracking process Download PDFInfo
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- CN100569921C CN100569921C CNB2006100469310A CN200610046931A CN100569921C CN 100569921 C CN100569921 C CN 100569921C CN B2006100469310 A CNB2006100469310 A CN B2006100469310A CN 200610046931 A CN200610046931 A CN 200610046931A CN 100569921 C CN100569921 C CN 100569921C
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Abstract
The present invention relates to a kind of single-stage hydrocracking process.With VGO and/or other heavy distillates is stock oil, adopts the single-stage hydrocracking technical process, under the hydrocracking operational condition, obtains various products.Wherein use the Hydrobon catalyst that comprises a kind of bulk phase catalyst on the top of single-stage hydrocracking catalyzer, bulk phase catalyst comprises composite oxides Ni
xW
yO
zWith oxide M oO
3, its weight ratio is 1: 10～10: 1.Compared with prior art, the inventive method keep that the single-stage hydrocracking technical process is simple, volume space velocity big and the prerequisite of advantage such as the plant construction investment is relatively low under, overcome its shortcoming, improved the adaptability that stock oil is changed, and the products production scheme is more flexible, and quality product is higher.
Description
Technical field
The present invention relates to a kind of single-stage hydrocracking process, particularly adopt high-activity hydrogenation catalyst, with two doses of (multi-agent) method for hydrogen cracking of single hop of vacuum distillate production cleaning light-end products.
Background technology
Along with the pay attention to day by day to environment protection, the requirement of environmental regulation is also more and more stricter.Motor tail gas has become the important source of pollution of topsoil, and is all the more so for big and medium-sized cities.Therefore, automotive fuel has been proposed higher quality limitations, the automotive fuel that is used for the city has been required strict more.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 that meets high quality requirement product from the production of poor heavy raw material oil, therefore hydrocracking technology has obtained attention in worldwide, and development has rapidly been arranged.
The maximum characteristics of hydrocracking process technology are can direct production not have high-quality petrochemical materialss such as cleaning automotive fuel such as the clean diesel of sulphur, low aromatic hydrocarbons, high hexadecane value, high-quality rocket engine fuel and light naphthar, heavy naphtha, tail oil.But also it is big to have a production handiness, characteristics such as liquid product yield height.From work flow, the simplest a kind of be single-stage hydrocracking technology (described herein single-stage hydrocracking technology does not comprise one-stage serial hydrocracking technology), the single-stage hydrocracking technology adopts anti-raw material impurity (sulphur, the nitrogen etc.) hydrocracking catalyst that ability is stronger, raw material is without hydrofining, directly carry out hydrocracking process, advantage such as have that technical process is simple, volume space velocity is big and the plant construction investment is relatively low.Simultaneously, single-stage hydrocracking has the high characteristics of intermediate oil yield.But the weak point of single-stage hydrocracking is that temperature of reaction is higher, and is unfavorable to aromatic hydrogenation reaction, and performance is that smoke point is lower to the influence of boat product of coal character, is that the cetane value increase rate is limited to the influence of product diesel oil character.And higher initial reaction temperature will cause the running period of device shorter, not be suitable for to do and heavy feed stock that nitrogen content is higher, and its handiness is subjected to bigger restriction.
Existing single-stage hydrocracking technology, all relate to a kind of making method of single-stage hydrocracking catalyzer as US3248318, US3923638, CN1253990, CN1508227, CN1508228, CN1566283, US4713167 relates to a kind of intermediate oil round-robin single-stage hydrocracking technology, the FR2830870 design is provided with the separating unit of flash separation ammonia between hydrofining reaction district and hydrocracking reaction district, US4172815 relates to a kind of single-stage hydrocracking process of producing boat coal and diesel oil.And more existing full scale plants, they the filling of catalyst reactor is required be, the loadings of hydrocracking catalyst has surpassed 80v%, remaining is protective material, transition agent and propping agent.Although these technology have the advantage of single-stage hydrocracking technology, also exist the stock oil bad adaptability simultaneously, the products production scheme is not the very flexible deficiency that waits.
US 4880526 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, US6652738 disclose a kind of VIII of containing family/group vib active metal component and have been used for bulk phase catalyst of hydrotreatment and preparation method thereof, in the Preparation of Catalyst that relates to, the moulding of catalyzer is adopted and prepared the metal-powder that contains Ni-Mo or Ni-Mo-W earlier, and is bonding or the metal-powder of Ni-Mo or Ni-Mo-W mixed dehydration afterwards, extrusion, drying with alumina gel with aluminum oxide again.Because the catalyst metal content height of this method preparation often lacks enough interactions and can cause catalyst strength poor between metal and aluminum oxide.Active ingredient part is made up of a large amount of metals, has some interior metal components and can not be fully utilized and cause loss of activity 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.
Owing to be subjected to crude oil to become the influence that heavily becomes bad day by day, the difficulty of the processing of cuts such as VGO also increases greatly, uses existing single-stage hydrocracking technology, operating severity further increases, make the catalyzer life cycle shorten, perhaps reduce treatment capacity, perhaps new device increases the loadings of catalyzer.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of single-stage hydrocracking technology, it can be under the prerequisite of advantages such as keeping that the single-stage hydrocracking technical process is simple, volume space velocity big and the plant construction investment is relatively low, overcome its shortcoming, improved the adaptability that stock oil is changed, and the products production scheme is more flexible, and quality product is higher.
It is generally acknowledged that in the single-stage hydrocracking technology, its catalyzer has anti-nitrogen, therefore can directly will directly not carry out hydrocracking reaction through hydrorefined raw material.But by the in-depth analysis of existing single-stage hydrocracking technology is learnt, though catalyzer has stronger nitrogen resistance in the single-stage hydrocracking technology, but at first the part catalyzer that contacts with not refining raw material is under the dense environment of organonitrogen, the acid sites of catalyzer (lytic activity center) is subjected to the strongly inhibited of organonitrogen, can not bring into play splitting action substantially.This part catalyzer generally only plays the effect of common catalyst for refining, promptly removes the impurity such as organonitrogen in the raw material, and after organonitrogen content in the logistics reduced, the hydrocracking catalyst of back was brought into play the cracking function gradually.That is to say that the nitrogen resistance of single-stage hydrocracking catalyzer is limited, just can not give full play of the hydrocracking performance when surpassing its anti-nitrogen limit, can only play common hydrofining effect.On the other hand, the single-stage hydrocracking catalyzer is not to design at the hydrofining purpose after all, its hydrofining performance and Hydrobon catalyst not as designing at the hydrofining purpose specially, and the cost of hydrocracking catalyst will be higher than Hydrobon catalyst.
According to top research, single-stage hydrocracking process of the present invention comprises following content:
(1) Hydrobon catalyst of hydroconversion reaction zone middle and upper part filling suitable proportion, reaction zone middle and lower part filling hydrocracking catalyst; (2) stock oil and hydrogen enter hydroconversion reaction zone, hydrogenation takes place on Hydrobon catalyst take off impurity reaction reactions such as () desulfurization, denitrogenation, deoxidation, aromatic hydrocarbons are full, directly contact through hydrorefined logistics, carry out hydrocracking and further take off reaction such as impurity with hydrocracking catalyst; (3) hydrocracking generates oil and enters high-pressure separator, and the hydrogen-rich gas of separating loops back reactor, and the liquid phase of separating enters fractionating system; (4) tail oil that obtains of fractionating system can be discharged system, also can all or part of circulation carry out hydrocracking.Wherein hydrocracking catalyst is the single-stage hydrocracking catalyzer of nitrogen-resistant type.Have a kind of bulk phase catalyst in the hydrogenation pretreatment catalyst at least, bulk phase catalyst contains Mo, W, three kinds of metal components of Ni, and wherein W, Ni 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%.(composition when above-mentioned catalyzer consists of oxidation state, catalyzer need to carry out sulfidizing by method well known to those skilled in the art in use)
The stock oil that the inventive method is used can be one or more of the VGO, the CGO that obtain in the oil, HGO, HCO etc., also can be coal tar, liquefied coal coil.
Reaction mass through the reaction conditions of hydrogenation pretreatment catalyst is: reaction pressure 4.0～20.0MPa, hydrogen to oil volume ratio are 300: 1～2500: 1, and the cumulative volume air speed is 0.1～6.0h
-1, 310 ℃～455 ℃ of temperature of reaction; Preferred operational condition is reaction pressure 5.0～19.0MPa, hydrogen to oil volume ratio 500: 1～2000: 1, volume space velocity 0.2～4.0h
-1, 320～445 ℃ of temperature of reaction.Reaction mass through the reaction conditions of hydrocracking catalyst is: reaction pressure 4.0～20.0MPa, hydrogen to oil volume ratio are 400: 1～3000: 1, and the cumulative volume air speed is 0.1～5.0h
-1, 310～455 ℃ of temperature of reaction; Preferred operational condition is reaction pressure 5.0～19.0MPa, hydrogen to oil volume ratio 500: 1～2500: 1, volume space velocity 0.2～4.0h
-1, 325 ℃～445 ℃ of temperature of reaction.
In the single-stage hydrocracking technology of the present invention, hydrogenation pretreatment catalyst can all be a bulk phase catalyst, also can be the combination of conventional hydrogenation pretreatment catalyst and bulk phase catalyst.During combination loading, the filling order of bulk phase catalyst and conventional hydrogenation pretreatment catalyst can be any, bulk phase catalyst can be seated in the top in refining reaction district, also can be seated in the bottom in pretreatment reaction district, 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.Wherein conventional hydrogenation pretreatment catalyst is the industrial catalyzer that generally adopts, as China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute develop 3936,3996, Hydrobon catalysts such as FF-16, FF-26, the function class that also can be external catalyst Co. exploitation is like catalyzer, HC-K, HC-P, HC-T as Uop Inc., KF-847, the KF-848 etc. of the TK-555 of Topsor company, TK-565 catalyzer and AKZO company.
Hydrocracking catalyst is preferably the single-stage hydrocracking catalyzer, is aluminum oxide, unformed silicon and molecular sieve etc. with the carrier generally, and molecular sieve content is generally 5%～60%, can select this commercial single-stage hydrocracking catalyzer, also can prepare on request.Commercial hydrocracking catalyst can be selected: the HC-12 of Uop Inc., HC-14, HC-24, HC-39 etc., the CR126 that CHEVRON company develops etc., Fushun Petrochemical Research Institute develop 3971,3974,3976, ZHC-01, ZHC-02, ZHC-04, FC-12, FC-14, FC-16, FC-26, FC-28 etc., wherein proper have ZHC-01, ZHC-02, ZHC-04, FC-14, FC-28, an ICR126 etc.The volume loadings of Hydrobon catalyst and hydrocracking catalyst is 2: 8～8: 2, is preferably 3: 7～7: 3.
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 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.The inventive method is not used 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 bulk phase catalyst, strengthened the hydrogenation performance of hydrogenation 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 improve the quality of hydrocracking product owing to improved the hydrofining degree of depth.
Description of drawings
Fig. 1 is a principle process flow diagram of the present invention.
Embodiment
Technical process of the present invention is the single-stage hydrocracking technical process, can adopt the one way pass-through mode, also can adopt the whole circulation process of tail oil part circulation process or tail oil.
The method particular content of single-stage hydrocracking technology of the present invention is as follows: with in VGO and other heavy distillate one or more is stock oil, under the hydrocracking operational condition, stock oil and hydrogen order by pretreatment catalyst and and hydrocracking catalyst, the generation oil that obtains separates in high-pressure separator, the gas circulation that obtains is used, 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.
In industrial operation, catalyzer can load in layering, and cold hydrogen inlet is arranged between each bed, injects cold hydrogen during operation, takes away the reaction heat that hydrogenation reaction and cracking reaction produce, and makes temperature of reaction control within the specific limits, makes operation safe, steady.Scale according to device can be used a reactor, also can use a plurality of reactors.Concrete grammar is a content well known to those skilled in the art.
Specifically technical process as shown in Figure 1: stock oil and hydrogen order by merging enter the pretreatment reaction district of all or part of bulk phase catalyst of filling, enter the reaction zone of filling hydrocracking catalyst then, 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 also can be with in the product one or more as the turning oil circulating reaction.
Bulk phase catalyst of the present invention obtains 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 of clear and definite benchmark is not 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.
Each catalyzer and the character of table 1 embodiment preparation
| 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 | 213 | 28.4 | 32.2 | 41.8 |
| MoO 3，wt％ | 16.5 | 57.6 | 18.6 | 28.1 | 17.0 |
| Al 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
Present embodiment is the specific embodiment of single-stage hydrocracking technology of the present invention.
Stock oil character sees Table 2, and the catalyst property that relates to sees Table 3, and processing condition and test-results see Table 4, and when adopting the tail oil cyclical operation, turning oil is＞350 ℃ of cuts.Oxidized catalyst is carried out conventional sulfidizing before use.As under the 15MPa 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-1 during liquid, 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 pretreatment 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 hydrogenation pretreatment catalyst, in hydrodenitrification, make the aromatic hydrocarbons degree of depth saturated, thereby promoted the quality of hydrocracking product relatively simultaneously.
Table 2 stock oil character
| The stock oil title | Grand celebration VGO | Iran VGO | VGO in the sand | Isolated island VGO |
| Density/gcm -3 | 0.8668 | 0.9027 | 0.9249 | 0.9138 |
| Boiling range/℃ | 299～529 | 335～542 | 337～539 | 350～560 |
| Sulphur content, m% | 0.12 | 1.28 | 2.53 | 0.77 |
| Nitrogen content/μ gg -1 | 340 | 1475 | 766 | 2300 |
| The BMCI value | 27.4 | 46.6 | 50.8 | 44.6 |
The main composition and the character of table 3 hydrogenation catalyst
| Catalyzer | FF-16 | FC-14 | FC-28 | ZHC-02 |
| Reactive metal is formed, w% | ||||
| WO 3 | 22.0 | 22.5 | 24.0 | |
| MoO 3 | 24.5 | |||
| NiO | 3.7 | 5.8 | 6.8 | 9.0 |
| P | 1.2 | |||
| Carrier | Surplus | Surplus | Surplus | Surplus |
| Shape | Trifolium | Cylinder | Cylinder | Cylinder |
| Pore volume/mlg -1 | 0.35 | ＞0.34 | ＞0.28 | 0.30 |
| Intensity/Nmm -1 | ＞14 | ＞18 | ＞18 | ＞12 |
| Specific surface area/m 2·g -1 | ＞160 | ＞160 | ＞170 | ＞210 |
Table 4 embodiment 5 processing condition and test-results
| The hydrocracking process condition | 1 | Reference example 1 | 2 | Reference example 2 |
| Technical process | One way is passed through | One way is passed through | ＞350 ℃ of recycle to extinctions | ＞350 ℃ of recycle to extinctions |
| Catalyzer | A/ZHC-02 | ZHC-02 | B/FC-14 | E/FC-14 |
| Stock oil | VGO in the sand | VGO in the sand | Iran VGO | Iran VGO |
| The catalyst loading volume ratio | 40∶60 | - | 45∶55 | 45∶55 |
| Pressure/MPa | 15.7 | 15.7 | 13.0 | 13.0 |
| Hydrogen to oil volume ratio | 800∶1/1200∶1 | 1200∶1 | 700∶1/1100 | 700∶1/1100 |
| Cumulative volume air speed/h -1 | 1.0 | 1.0 | 0.8 | 0.8 |
| Temperature/℃ | 397/407 | 415 | 390/400 | 395/402 |
| The heavy naphtha yield, % | 7.2 | 6.9 | 10.5 | 11.2 |
| The heavy naphtha virtue is dived | 55.4 | 53.1 | 49.5 | 49.1 |
| The boat yield of coal, % | 33.2 | 34.4 | 37.0 | 38.2 |
| Boat coal smoke point/mm | 27 | 26 | 27 | 25 |
| Diesel yield, % | 39.1 | 38.1 | 45.7 | 44.9 |
| Diesel cetane-number | 64.5 | 62.4 | 66.4 | 65.8 |
| The tail oil yield, % | 18.1 | 18.5 | - | - |
| Tail oil BMCI value | 11.9 | 13.5 | - | - |
Continuous table 4 embodiment 5 processing condition and test-results
| The hydrocracking process condition | 3 | 4 | 5 |
| Technical process | One way is passed through | One way is passed through | ＞350 ℃ of recycle to extinctions |
| Stock oil | Grand celebration VGO | VGO in the sand | Isolated island VGO |
| Catalyzer | FF-16/C/FC-28 | C/FC-14 | D/FC-14 |
| The catalyst loading volume ratio | 30∶30∶40 | 30∶70 | 40∶60 |
| Pressure/MPa | 12.5 | 8.0 | 13.7 |
| Temperature/℃ | 382/382/392 | 386/388 | 385/398 |
| Cumulative volume air speed/h -1 | 1.4 | 0.5 | 1.1 |
| Hydrogen to oil volume ratio | 900∶1/900∶1/1300∶1 | 1000∶1/1500∶1 | 700∶1/1100 |
| The heavy naphtha yield, % | 6.6 | 9.5 | 13.9 |
| The heavy naphtha virtue is dived | 44.2 | 41.2 | 55.6 |
| The boat yield of coal, % | 26.4 | 20.4 | 42.9 |
| Boat coal smoke point/mm | 27 | 23 | 26 |
| Naphthalene is a hydrocarbon, % | - | 0.04 | - |
| Diesel yield, % | 37.1 | 27.4 | 36.4 |
| Diesel cetane-number | 61.1 | 52.4 | 63.0 |
| The tail oil yield, % | 25.1 | 35.5 | - |
| Tail oil BMCI value | 9.5 | 12.4 | - |
Claims (10)
1, a kind of single-stage hydrocracking process comprises following content: the hydrogenation pretreatment catalyst of (1) hydroconversion reaction zone middle and upper part filling suitable proportion, reaction zone middle and lower part filling hydrocracking catalyst; (2) stock oil and hydrogen enter hydroconversion reaction zone, hydrogenation takes place on hydrogenation pretreatment catalyst take off the impurity reaction, directly contact with hydrocracking catalyst through hydrorefined logistics, carry out hydrocracking and further take off the impurity reaction; (3) hydrocracking generates oil and enters high-pressure separator, and the hydrogen-rich gas of separating recycles, and the liquid phase of separating enters fractionating system; Wherein have a kind of bulk phase catalyst in the hydrogenation pretreatment catalyst at least, bulk phase catalyst contains Mo, W, three kinds of metal components of Ni, and W, Ni are with Ni in the oxidized catalyst
xW
yO
z, the composite oxides form of z=x+3y exists, and Mo is with MoO
3Oxide form exists; 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%.
2, in accordance with the method for claim 1, it is characterized in that described 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, it is characterized in that the tail oil discharge system that described fractionating system obtains, or hydrocracking is carried out in all or part of circulation.
4, in accordance with the method for claim 1, it is characterized in that reaction mass through the reaction conditions of hydrogenation pretreatment catalyst is: reaction pressure 4.0～20.0MPa, hydrogen to oil volume ratio are 300: 1～2500: 1, and the cumulative volume air speed is 0.1～6.0h
-1, 310 ℃～455 ℃ of temperature of reaction; Reaction mass through the reaction conditions of hydrocracking catalyst is: reaction pressure 4.0～20.0MPa, hydrogen to oil volume ratio are 400: 1～3000: 1, and the cumulative volume air speed is 0.1～5.0h
-1, temperature of reaction 3 10～～455 ℃.
5, in accordance with the method for claim 1, it is characterized in that reaction mass through the reaction conditions of hydrogenation pretreatment catalyst is: reaction pressure 5.0～19.0MPa, hydrogen to oil volume ratio 500: 1～2000: 1, volume space velocity 0.2～4.0h
-1, 320～445 ℃ of temperature of reaction; Reaction mass through the reaction conditions of hydrocracking catalyst is: reaction pressure 5.0～～19.0MPa, hydrogen to oil volume ratio 500: 1～2500: 1, volume space velocity 0.2～4.0h
-1, 325 ℃～445 ℃ of temperature of reaction.
6, in accordance with the method for claim 1, the volume ratio that it is characterized in that described hydrogenation pretreatment catalyst and hydrocracking catalyst is 2: 8～8: 2.
7, in accordance with the method for claim 1, the volume ratio that it is characterized in that described hydrogenation pretreatment catalyst and hydrocracking catalyst is 3: 7～7: 3.
8, in accordance with the method for claim 1, it is characterized in that described hydrogenation pretreatment catalyst all is a bulk phase catalyst
Or the combination of conventional hydrogenation pretreatment catalyst and bulk phase catalyst
During combination loading, the volume ratio of bulk phase catalyst and conventional catalyst is 90: 10～10: 90.
9, in accordance with the method for claim 1, it is characterized in that described hydrocracking catalyst is the single-stage hydrocracking catalyzer.
10, in accordance with the method for claim 1, the specific surface area that it is characterized in that described bulk phase catalyst is 120～400m
2/ g, pore volume are 0.10～0.50ml/g.
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| CN109988603B (en) * | 2017-12-29 | 2021-07-09 | 中国石油化工股份有限公司 | Hydrogenation coupling process for producing low-freezing-point diesel oil |
| CN109988618B (en) * | 2017-12-29 | 2021-05-04 | 中国石油化工股份有限公司 | Flexible single-stage two-agent hydrocracking process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002004117A1 (en) * | 2000-07-12 | 2002-01-17 | Akzo Nobel N.V. | Process for preparing an additive-based mixed metal catalyst |
| US6537442B1 (en) * | 1998-06-29 | 2003-03-25 | Akzo Nobel N.V. | Cogel containing oxidic compounds of tetravalent, trivalent, and divalent metallic elements |
| US6635599B1 (en) * | 1997-07-15 | 2003-10-21 | Exxonmobil Research & Engineering Company | Mixed metal catalyst, its preparation by co-precipitation, and its use |
| CN1458237A (en) * | 2002-05-15 | 2003-11-26 | 中国石油化工股份有限公司 | Method for hydrogen cracking |
| CN1526478A (en) * | 1999-01-15 | 2004-09-08 | ��˹��ŵ�� | Mixed metal catalyst and use thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6635599B1 (en) * | 1997-07-15 | 2003-10-21 | Exxonmobil Research & Engineering Company | Mixed metal catalyst, its preparation by co-precipitation, and its use |
| US6537442B1 (en) * | 1998-06-29 | 2003-03-25 | Akzo Nobel N.V. | Cogel containing oxidic compounds of tetravalent, trivalent, and divalent metallic elements |
| CN1526478A (en) * | 1999-01-15 | 2004-09-08 | ��˹��ŵ�� | Mixed metal catalyst and use thereof |
| WO2002004117A1 (en) * | 2000-07-12 | 2002-01-17 | Akzo Nobel N.V. | Process for preparing an additive-based mixed metal catalyst |
| CN1458237A (en) * | 2002-05-15 | 2003-11-26 | 中国石油化工股份有限公司 | Method for hydrogen cracking |
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