CN1955262A - Two-stage hydrocracking method - Google Patents
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- CN1955262A CN1955262A CN 200610008418 CN200610008418A CN1955262A CN 1955262 A CN1955262 A CN 1955262A CN 200610008418 CN200610008418 CN 200610008418 CN 200610008418 A CN200610008418 A CN 200610008418A CN 1955262 A CN1955262 A CN 1955262A
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Abstract
This invention discloses a poor quality catalytic cracking diesel hydrogenation method. This invention includes two stages hydrocracking dealing with catalytic cracking diesel, especially the poor quality catalytic cracking diesel from catalytic hydrogen transfer process. The density of the related poor quality catalytic cracking diesel is 0.90g/ml at 20deg.C, and its aromatic hydrocarbon is over 60wt%, and the value of hexadecane is less than 30. Mixing poor quality catalytic cracking diesel and heavy cracking material and conducting hydrogenation, hydrocracking is conducted after removal of sulphur, nitrogen and other impurities from reaction oil. It is a sufficient utilization of the feature that low hydrogen and high aromatic hydrocarbon content of catalytic cracking diesel to produce Gaofangqian heavy naphtha in order to realize the effective utilization of the poor quality catalytic cracking diesel.
Description
Technical field
The present invention relates to a kind of method for hydrogen cracking, particularly relate to a kind of method for hydrogen cracking that can effectively handle poor quality catalytic cracking diesel.
Background technology
Along with crude oil heaviness, poor qualityization day by day, and to the minimizing of market to the heavy oil demand, to the increase of light oil demand, the degree of depth transforming degree of heavy residual oil improves constantly.Wherein catalytic cracking is one of important means of heavy residual oil lighting.But the product characteristics that catalytic cracking obtains is generally relatively poor, needs just can obtain qualified product through further processing again.In general the diesel oil distillate that catalytic cracking obtains has the aromaticity content height, and cetane value is low, and characteristics such as sulphur, nitrogen content height are difficult to directly as product, and common processing means also is difficult to effectively improve its quality product.
The common method of processing poor quality catalytic cracking diesel is hydrofining at present, and this technology investment is low, technology maturation, but the improvement of diesel oil is had certain restriction, generally diesel-fuel cetane number can only be improved 3-5 unit.The hydrofining technology of the employing routine of introducing as US6129835, though can effective elimination sulphur, impurity such as nitrogen, obviously to improve the color and the stability of diesel product, and keep very high diesel yield, diesel product cetane value amplification is limited.If adopt severe condition hydrofining, because hydrofining does not change the molecular structure of petroleum fractions substantially, cetane value can not be greatly improved, and because hydrogen consumption huge (more than the 4wt%), tooling cost significantly increases.
US5114562 and US5068025 etc. adopt two-stage method diesel oil hydrogenation treatment process, one section adopts traditional Hydrobon catalyst with impurity removals such as the sulphur in the raw material, nitrogen, and the hydrogenation catalyst that second section use has high hydrogenation saturated activity carries out deeply de-aromatizing.Though this technology can be taken off the aromatic hydrocarbons in the diesel oil very low degree, the hydrogen consumption is big, and investment is high, and is less economical, and cetane value improves not obvious, can not obtain qualified diesel product.
Middle pressure hydrocracking or MHUG (as patent US4971680, CN1171430A etc.) utilize hydrocracking catalyst catalytic cracking diesel oil to be carried out the processing of certain transformation efficiency, this method can improve the cetane value of catalytic cracking diesel oil ten more than the unit, and obtain the gasoline products of certain yield, but, still can not obtain qualified diesel product for the very low poor quality catalytic cracking diesel of raw material cetane value.
It is to select shape cracked technological process under hydrogen and the middle pressure condition facing that CN 1061679C has introduced the hydrodewaxing technology.It utilizes the pore passage structure of particular molecule sieve catalyst uniqueness and suitable acid sites, and the contour condensation point component of the normal paraffin in the diesel feed is carried out selective splitting, and to reduce the zero pour of diesel product, the while by-product is gasoline and C partly
3, C
4Lighter hydrocarbons.CN1257107A has introduced hydrogenation pour point depression technology.This technology adopts hydrofining-hydrodewaxing combination process flow process, by the hydrogenation pre-refining is carried out in charging, not only improved hydrodewaxing section feeding quality, improved adaptability to stock oil, prolonged the running period of device, and alleviated operational condition greatly, and the purpose quality product is greatly improved.Adopt the above-mentioned technology can the higher diesel oil distillate raw material of pour point depression wax content, can not be used to process the high poor quality catalytic cracking diesel US5030780 of aromaticity content and use the catalyst treatment diesel oil that contains Y zeolite and amorphous silicon aluminium, mainly carry out saturated to the aromatic hydrocarbons in the diesel oil, but it is limited that cetane value improves, for the extremely low poor quality catalytic cracking diesel raw material of cetane value, still can not obtain the product that closes.CN1156752A discloses a kind of diesel modifying technology, use hydrocracking catalyst, under the condition of a certain amount of nitrogen of control, make the aromatic hydrocarbons in the diesel oil carry out ring-opening reaction, can obviously improve diesel-fuel cetane number, generally cetane value can be improved 10 more than the unit.But when being used for the extremely low poor quality catalytic cracking diesel of cetane value, still can not obtain qualified product.US5011593 introduces a kind of sweetening process that is used for sulphur and the higher raw material of aromatic hydrocarbons amount, uses the catalyzer contain the β zeolite, and using the sulphur content of raw material is 0.5～5.0wt%, more than the aromaticity content 50wt%, as the light cycle oil of catalytic cracking etc.This patent is equivalent to adopt and contains beta-zeolite catalyst the catalytic cracking light cycle oil is carried out mild hydrocracking, for the extremely low poor quality catalytic cracking diesel of cetane value, can not obtain qualified product.
US4789457, US4919789 carry out catalytic cracking with heavy feed stock, are raw material with the catalytic cracking light cycle oil, adopt middle pressure hydrocracking to produce gasoline.US4426276 carries out catalytic cracking with the crude oil heavy ends to be handled, and catalytic cracking light cycle oil and heavy cycle oil mix with straight run intermediate oil (straight-run diesel oil) and carries out hydrocracking, and purpose is a production gasoline.The main purpose of these technology is produced Fuel Petroleum, fails to make full use of the high characteristics of catalytic cracking turning oil aromaticity content.
Along with the development of catalytic cracking technology, new technology can reduce the olefin(e) centent in the catalytically cracked gasoline, as catalytic hydrogen transfer technology (as described in CN1310223A etc.).The reduction of olefin(e) centent means the increase of hydrogen richness in the gasoline, hydrogen richness in the catalytic cracking diesel oil that consequently obtains reduces, promptly be equivalent to hydrogen " transfer " in the diesel oil in gasoline, therefore the quality of gained catalytic cracking diesel oil is poorer, the character that shows is that aromaticity content increases, generally can reach more than the 60wt%, particularly the content of condensed-nuclei aromatics increases more; The increase of condensed-nuclei aromatics content causes diesel oil density to raise, and generally can reach more than 0.90～0.99g/ml, and cetane value reduces, usually less than 30.Though this class poor quality catalytic cracking diesel also can adopt aforesaid method to handle, the hydrogenation process hydrogen consumption that this class diesel oil is converted into proper fuel is huge, all more than 4w%, causes production cost too high usually, does not have advantage economically.
Summary of the invention
At the deficiencies in the prior art, the invention provides the hydrocracking process of a kind of processing poor quality catalytic cracking diesel (LCO).The present invention carries out comprehensive treating process with poor quality catalytic cracking diesel and heavy hydrogenated cracking stock, to realize such poor quality is urged the reasonable utilization of bavin.
Method for hydrogen cracking of the present invention is:
A, poor quality catalytic cracking diesel are mixed with the heavy hydrogenated cracking stock, and enter the hydrotreatment district, remove impurity such as sulphur, nitrogen under hydroprocessing condition; The two blending ratio is 1: 20～20: 1 (wt), is suitably 1: 10～5: 1; Described poor quality catalytic cracking diesel is attached most importance to, the residual oil catalytic cracking process diesel oil that obtains of catalytic hydrogen transfer process especially, and this diesel oil hydrogen richness is low, and 20 ℃ of density can reach more than the 0.90g/ml, are generally 0.90～0.99g/ml, are generally 0.91～0.97g/ml; Aromaticity content can reach more than the 60wt%, is generally 60～97wt%, is generally 70～90wt%; Cetane value is about 20, be generally＜30, be generally 12～25;
The effluent of b, step a carries out gas-liquid separation, and liquid product enters hydrocracking zone after gas is carried, and carries out cracking under hydrocracking condition;
The effluent of c, step b is after gas-liquid separation, and liquid product enters separation column to be separated, and obtains light-end products and tail oil.
Heavy hydrogenated cracking stock oil of the present invention is generally vacuum gas oil (VGO), can also comprise one or more of straight-run gas oil (AGO), wax tailings (CGO), heavy catalytic cycle oil (HCO) and deasphalted oil (DAO), coal synthetic oil or coal tar usually.The raw material that enters hydrocracking zone can also comprise other refining distillate except the effluent in hydrotreatment district, as refined products of cycloalkyl straight-run diesel oil, coker gas oil and residual hydrogenation diesel oil etc.
The employed catalyzer of the described hydrotreatment of step a generally includes protective material and Hydrobon catalyst, and described hydroprocessing condition is: hydrogen dividing potential drop 4～18MPa, 320～480 ℃ of temperature, air speed 0.1～8.0h
-1, hydrogen to oil volume ratio 300: 1～2500: 1.
The described hydrocracking condition of step b is: hydrogen dividing potential drop 3～20MPa, 280～480 ℃ of temperature, air speed 0.1～8.0h
-1, hydrogen to oil volume ratio 300: 1～2500: 1; Preferred hydrocracking condition is: hydrogen dividing potential drop 4～17MPa, 300～440 ℃ of temperature, air speed 0.5～5.0h
-1, hydrogen to oil volume ratio 500: 1～2000: 1.
The described separation column of step c can adopt conventional operational condition, can fractionate out light naphthar, heavy naphtha, boat coal, diesel oil and tail oil as required.
The working pressure of hydrotreatment district and hydrocracking zone can be identical, also can be different, preferred hydrocracking zone in depress and operate.Hydrotreatment and hydrocracking use two to overlap independently recycle hydrogen system respectively.
Compared with prior art, the present invention has following characteristics:
The present invention adopts two-stage hydrocracking technology to handle poor quality catalytic cracking diesel.Owing to removed heteroatoms and dissolved ammonia such as sulphur, nitrogen in the cracking zone charging, so the activity of Nobel metal hydrogen cracking catalyst can be given full play to.Cracking zone can be operated under lower hydrogen dividing potential drop, higher air speed or lower temperature, thereby can preserve the aromatic hydrocarbons in the heavy naphtha.And the high hydrogenation activity of noble metal catalyst has guaranteed that then the aromaticity content in rocket engine fuel and the diesel oil can satisfy specification of quality, and the BMCI value of tail oil is also lower simultaneously; Parallel feeding is through hydrocracking, and the aromatic hydrocarbons in the poor quality catalytic cracking diesel basic " transfer " has arrived in the heavy naphtha, has therefore also guaranteed the arene underwater content very high (can reach more than the 70wt%) of heavy naphtha.If cooperate suitable catalyzer, then can realize the maximum production of chemical industry with petroleum naphtha.The inventive method has been given full play to the characteristics of two-stage hydrocracking technology, utilizes the poor quality catalytic cracking diesel that hydrogen richness is low, aromaticity content is high to produce the fine reformer feed, has realized the effective processing to such poor quality catalytic cracking diesel.
Description of drawings
Fig. 1 is a principle process flow diagram of the present invention.
Embodiment
The employed catalyzer in hydrotreatment of the present invention district can be existing various conventional Hydrobon catalysts.Hydrobon catalyst is made up of carrier and the hydrogenation component that is loaded in above it usually.Carrier generally is selected from inorganic refractory oxide, as aluminum oxide, amorphous silicon aluminium, silicon oxide, titanium oxide or contain different elements such as the aluminum oxide of P, B, F etc. etc.; Hydrogenation component is group vib and the VIII family metal component that is selected from the periodic table of elements, generally is selected among W, Mo, Ni, the Co one or more.Weight with catalyzer is benchmark, WO
3Or MoO
3Content be generally 10wt%～35wt%, preferred 15wt%～30wt%, the content of NiO is 3wt%～10wt%.Specifically can select existing Hydrobon catalyst, perhaps be prepared as required.Commercial Hydrobon catalyst mainly contains: the HC-K of Uop Inc., HC-T, HC-P and FRIPP 3936,3996, FF-16, FF-26 etc.
The hydrocracking catalyst that the present invention uses is noble metal catalyst, can be to comprise any suitable Nobel metal hydrogen cracking catalyst of prior art, the dual-function catalyst that it is made up of hydrogenation component and acidic components.Hydrogenation component is selected from one or more among Rh, Ru, Pd, Os, Ir, the Pt usually, one or both among Pd and the Pt preferably, and acidic components are generally Y zeolite or Modified Zeolite Y.Weight with catalyzer is benchmark, and Pd is or/and the content of Pt is 0.05wt%～2.0wt%, and the content of Y zeolite is 5wt%～95wt%, and surplus is a binding agent.Usually can also comprise base metal in the noble metal catalyst, described precious metal is one or more among Ni, Co or the Mo.
The Nobel metal hydrogen cracking catalyst that the present invention recommends composed as follows:
Pd is or/and Pt 0.05wt%～2.0wt%;
Modified Y zeolite 5wt%～95wt%;
The tackiness agent surplus.
The specific surface area of described Nobel metal hydrogen cracking catalyst is 350～700m
2/ g, pore volume are 0.35～0.65ml/g.The base metal that wherein comprises 0.5wt%～10wt% in the modified Y zeolite, its sial weight ratio is 5.5～50, unit cell parameters is 2.430～2.455nm.
This hydrocracking catalyst can adopt a kind of preparation the in following two kinds of methods:
The preparation method one: modified Y zeolite add mix behind tackiness agent, the extrusion aid pinch, roll, extruded moulding, and drying and roasting obtain containing the carrier of modified Y zeolite; Water-soluble solution impregnated carrier with containing precious metal at room temperature dries then naturally, drying, and roasting obtains the catalyzer finished product.
The preparation method two: modified Y zeolite carries out the precious metal ion exchange, the secondary hydrothermal treatment consists, and ammonium ion exchange, washing, drying are filtered in pickling then; Add mix behind tackiness agent, the extrusion aid pinch, roll, extruded moulding, and drying and roasting obtain the catalyzer finished product.
The preparation method of wherein said modified Y zeolite is: be raw material with NaY, carry out ion-exchange with non-noble metal water soluble salt, actual conditions is: regulate pH value to 2～8 with acid or ammoniacal liquor, with non-noble metal water soluble salt exchange 1～5 time; Last exchange back is with distilled water wash 1～3 time, and 100～150 ℃ of dryings, dried zeolite carries out hydrothermal treatment consists then, and washing is filtered in ammonium ion exchange, pickling, and 100～150 ℃ of dryings 1～48 hour, promptly obtains described modified Y zeolite.
In this Nobel metal hydrogen cracking catalyst, because the base metal dispersity height that gets on of ion-exchange, and precious metal played further buffer action, make the precious metal dispersity further improve.Simultaneously, because contained base metal itself is a kind of hydrogenation active metals, and base metal hydrogenation activity under the situation of sulfur-bearing is higher, therefore the catalyzer that contains modified Y zeolite with the technical program preparation has higher activity and selectivity, is particularly useful for the two-stage hydrocracking maximum and produces in the technology of petroleum naphtha.
Further explain technical solution of the present invention below by embodiment.The used Nobel metal hydrogen cracking catalyst of embodiment 1～4 preparation the present invention, catalyst property is listed in table 1.Embodiment 5～8 is the technological test and the effect of the inventive method, and process flow diagram is seen Fig. 1.Wherein stock oil character is listed in table 2, and the character of FF-26 catalyzer is listed in table 3, and processing condition and product property are listed in table 4.
In embodiments of the present invention, the boiling range scope of each cut is: 65～177 ℃ of heavy naphtha, 177～282 ℃ in boat coal, 282～350 ℃ of diesel oil, tail oil 350
+℃.
Embodiment 1
Get a certain amount of nickelous nitrate and be dissolved in water, be mixed with the solution that concentration is 10gNiO/100ml, the above-mentioned aqueous solution adding distil water of 70ml is diluted to 1000ml, add 250g NaY zeolite (butt 80wt%), be heated to 70 ℃ of exchanges 2 hours.Repeated exchanged 2 times after the 2nd exchange, is filtered washing 3 times, then in 110 ℃ of dryings 8 hours, and puts into 550 ℃ of roastings of hydrothermal treatment consists stove 6 hours, and steam partial pressure is 0.05MPa.Y zeolite after the hydrothermal treatment consists is put into 1000ml 1N ammonium nitrate/aqueous nitric acid (pH=2) carries out ammonium exchange, pickling 2 hours, 70 ℃ of temperature, pickling after-filtration washing 3 times, then in 110 ℃ of dryings 8 hours, modified Y zeolite.
With above-mentioned modified Y zeolite 140g (butt 86wt%) and 150g tackiness agent (SB-Al
2O
3Be prepared from tackiness agent butt 20wt% with an amount of rare nitric acid making beating) mix and pinch, extruding diameter is 1.5mm cylinder bar, 110 ℃ of dryings, 550 ℃ of roastings 4 hours must contain the carrier of modified Y zeolite.
Get a certain amount of Pd (NH
3)
4Cl
2Be dissolved in water, being mixed with concentration is to contain Pd solution l.0g/100ml, and that gets that above-mentioned preparation method obtains contains modified Y zeolite carrier 100g, contain the Pd solution impregnation with 80ml, dipping time is 6 hours, floods back 110 ℃ of dryings, 550 ℃ of roastings 4 hours, catalyzer C-1.
Embodiment 2
Get a certain amount of Xiao Suangu and be dissolved in water, be mixed with the solution that concentration is 10gCoO/100ml, the above-mentioned solution adding distil water of 150ml is diluted to 1000ml, add 250g NaY zeolite (butt 80wt%), be heated to 90 ℃ of exchanges 2 hours.Repeated exchanged 2 times after the 2nd exchange, is filtered washing 3 times, then in 110 ℃ of dryings 4 hours, and puts into 650 ℃ of roastings of hydrothermal treatment consists stove 4 hours, and steam partial pressure is 0.15MPa.Y zeolite after the hydrothermal treatment consists is put into 1000ml 1N ammonium nitrate/aqueous nitric acid (pH=2) carries out ammonium exchange, pickling 4 hours, 90 ℃ of temperature, pickling after-filtration washing 3 times, then in 110 ℃ of dryings 8 hours, modified Y zeolite.
With above-mentioned modified Y zeolite 117g (butt 90wt%) and 225g tackiness agent (SB-Al
2O
3Be prepared from tackiness agent butt 20wt% with an amount of rare nitric acid making beating) to mix and pinch, extrusion gets diameter 1.5mm cylinder bar, 110 ℃ of dryings, 500 ℃ of roastings 4 hours must contain the carrier of modified Y zeolite.
Get a certain amount of PdCl
2The enriching dissolving with hydrochloric acid, and thin up to become concentration be the H that contains Pd 0.5g/100ml
2PdCl
4Solution is got the carrier 100g that contains modified Y zeolite, and with the above-mentioned solution of 60ml saturated dipping, the time is 6 hours, floods back 110 ℃ of dryings, 600 ℃ of roastings 4 hours, catalyzer C-2.
Embodiment 3
Get a certain amount of ammonium molybdate and be dissolved in water, being mixed with concentration is 10gMoO
3The solution of/100ml is diluted to 1000ml with the above-mentioned solution adding distil water of 25ml, adds 250g NaY zeolite (butt 80 heavy %), is heated to 60 ℃ of exchanges 4 hours.Repeated exchanged 2 times after the 2nd exchange, is filtered washing 3 times, then in 110 ℃ of dryings 4 hours, and puts into 500 ℃ of roastings of hydrothermal treatment consists stove 6 hours, and steam partial pressure is 0.15MPa.Y zeolite after the hydrothermal treatment consists is put into 1000ml 1N ammonium nitrate/aqueous nitric acid (pH=2) carries out ammonium exchange, pickling 4 hours, 60 ℃ of temperature, pickling after-filtration washing 3 times, then in 110 ℃ of dryings 8 hours, modified Y zeolite.
With above-mentioned modified Y zeolite 139g (butt 92wt%) and 113g tackiness agent (SB-Al
2O
3Be prepared from tackiness agent butt 20wt% with an amount of rare nitric acid making beating) mix and pinch, extrusion gets diameter 1.5mm cylinder bar, 110 ℃ of dryings, 600 ℃ of roastings 4 hours contain the modified Y zeolite carrier.
Get a certain amount of Pt (NH
3)
4(NO
3)
2Be dissolved in water, be mixed with concentration, get the above-mentioned carrier 100g that contains modified Y zeolite, with 150ml Pt (NH for containing Pt 1.0g/100ml solution
3)
4(NO
3)
2Solution impregnation catalyst, dipping time is 12 hours, floods back 110 ℃ of dryings, 500 ℃ of roastings 6 hours.Get catalyzer C-3.
Embodiment 4
Get a certain amount of nickelous nitrate and be dissolved in water, being mixed with concentration is that 10g/100ml contains NiO solution, and the above-mentioned solution adding distil water of 70ml is diluted to 1000ml, adds 250g NaY zeolite (butt 80m%), is heated to 70 ℃ of exchanges 2 hours.Repeated exchanged 2 times after the 2nd exchange, is filtered washing 3 times, then in 110 ℃ of dryings 8 hours, and puts into 550 ℃ of roastings of hydrothermal treatment consists stove 6 hours, and steam partial pressure is 0.05MPa.Y zeolite after the hydrothermal treatment consists is put into 1000ml 1N ammonium nitrate/aqueous nitric acid (pH=2) carries out ammonium exchange, pickling 4 hours, 70 ℃ of temperature, pickling after-filtration washing 3 times, then in 110 ℃ of dryings 8 hours, modified Y zeolite.
Get a certain amount of Pd (NH
3)
4Cl
2Be dissolved in water, being mixed with concentration is the solution that contains Pd 1.0g/100ml, the above-mentioned aqueous solution adding distil water of 200ml is diluted to 1000ml, add the above-mentioned hydrothermal treatment consists post-modification of 200g Y zeolite, be heated to 60 ℃, stir exchange 2 hours down at 60 ℃, filter washing 3 times then, the 3rd washing back is in 110 ℃ of dryings 4 hours, and puts into 550 ℃ of roastings of hydrothermal treatment consists stove 6 hours, and steam partial pressure is 0.05MPa.Y zeolite after the secondary hydrothermal treatment consists is put into 1000ml 1N ammonium nitrate/aqueous nitric acid (pH=2) carries out ammonium exchange, pickling 4 hours, 90 ℃ of temperature, pickling after-filtration washing 3 times, then in 110 ℃ of dryings 8 hours, contain the modified Y zeolite of Ni, Pd simultaneously.
With the above-mentioned modified Y zeolite 133g (butt 90wt%) and 150g tackiness agent (SB-Al that contains Ni, Pd simultaneously
2O
3Be prepared from tackiness agent butt 20wt% with an amount of rare nitric acid making beating) mix and pinch, extrusion gets diameter 1.5mm cylinder bar, 110 ℃ of dryings, 550 ℃ of roastings 4 hours, catalyzer C-4.
The composition of table 1 hydrocracking catalyst and character
| The catalyzer numbering | C-1 | C-2 | C-3 | C-4 |
| Form, wt% Pd Pt modified Y zeolite specific surface, m 2/ g pore volume, ml/g modified Y zeolite character base metal, wt% SiO 2/Al 2O 3, wt% unit cell parameters, nm | 0.81 - 80 570 0.394 NiO 4.02 9.75 2.445 | 0.29 - 70 568 0.404 CoO 10.00 7.23 2.447 | - 1.47 85 528 0.378 MoO 3 1.43 9.56 2.440 | 0.79 - 80 395 0.348 NiO 8.64 12.36 2.432 |
Table 2 stock oil character
| Stock oil | Iran VGO | Catalytic cracking diesel oil 1 | Catalytic cracking diesel oil 2 |
| Density/gcm -3Boiling range/℃ sulphur content, wt% nitrogen content/μ gg -1Aromatic hydrocarbons, the wt% cetane value | 0.9135 350～545 1.74 1535 43.8 - | 0.9458 168～369 1.12 915 82.0 16.6 | 0.9694 202～361 1.18 1620 93.1 13.5 |
Table 3FF-26 catalyst property
| Chemical constitution/wt% | |
| MoO 3 NiO P 2O 5 Al 2O 3Pore volume/mlg -1Specific surface area/m 2·g -1 | 25.2 3.8 1.1 surpluses 0.34 175 |
Table 4 processing condition and product property
| Project | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Hydrofinishing section feedstock oil catalyst pressure/MPa temperature/℃ volume space velocity/h-1Hydrogen to oil volume ratio treated oil nitrogen content/μ gg -1Hydrocracking section stock oil catalyzer pressure/MPa temperature/℃ volume space velocity/h -1Hydrogen to oil volume ratio product yield and character heavy naphtha yield, wt% heavy naphtha virtue submerge yield of coal, wt% | VGO/ urges bavin 1=80/20 FF-26 15.0 375 1.1 refining to generate oily C-1 15.0 370 1.5 900: 1 40.6 74.5 18.0 in 900: 1 18.0 | VGO/ urges bavin 1=70/30 FF-26 10.0 380 1.1 refining to generate oily C-2 10.0 382 1.3 1200: 1 37.8 74.6 21.6 in 1000: 1 3.1 | VGO/ urges bavin 2=75/25 FF-26 12.0 378 1.0 refining to generate oily C-3 12.0 380 1.8 1000: 1 37.1 73.5 20.5 in 800: 1 12.5 | VGO/ urges bavin 2=85/15 FF-26 7.0 382 0.8 1000: the 1 6.0 refining oily C-4 7.0 365 1.2 1500: 1 34.5 76.8 16.4 of generation |
| Boat coal smoke point/mm diesel yield, wt% diesel cetane-number tail oil yield, wt% tail oil BMCI value | 26 10.5 59.8 20.3 6.7 | 25 18.5 54.2 12.1 9.3 | 26 13.6 56.7 19.8 8.5 | 25 9.8 53.4 29.5 12.4 |
Claims (13)
1, a kind of poor quality catalytic cracking diesel method for hydrogen cracking comprises the steps:
A, poor quality catalytic cracking diesel are mixed with the heavy hydrogenated cracking stock, and enter the hydrotreatment district, remove impurity such as sulphur, nitrogen under hydroprocessing condition, and wherein the two weight ratio of mixture is 1: 20～20: 1;
The effluent of b, step a carries out gas-liquid separation, and liquid product enters hydrocracking zone after gas is carried, and carries out cracking under hydrocracking condition;
The effluent of c, step b is after gas-liquid separation, and liquid product enters separation column to be separated, and obtains light-end products and tail oil.
2, method for hydrogen cracking according to claim 1 is characterized in that, 20 ℃ of density of described poor quality catalytic cracking diesel are more than the 0.90g/ml, and more than the aromaticity content 60wt%, cetane value is about 20.
3, method for hydrogen cracking according to claim 1 is characterized in that, described weight ratio of mixture is 1: 10～5: 1.
4, method for hydrogen cracking according to claim 1 and 2 is characterized in that, the density that described poor quality catalytic cracking diesel is 20 ℃ is 0.90～0.99g/m, and aromaticity content is 60～97wt%, and cetane value is less than 30.
5, method for hydrogen cracking according to claim 1 is characterized in that, described poor quality catalytic cracking diesel is attached most importance to, the residual oil catalytic cracking process diesel oil that obtains of catalytic hydrogen transfer process especially.
6, method for hydrogen cracking according to claim 1, it is characterized in that described heavy hydrogenated cracking stock comprises one or more of vacuum gas oil, straight-run gas oil, wax tailings, heavy catalytic cycle oil, deasphalted oil, coal synthetic oil or coal tar.
7, method for hydrogen cracking according to claim 1 is characterized in that, described hydroprocessing condition is: hydrogen dividing potential drop 4～18MPa, 320～480 ℃ of temperature, volume space velocity 0.1～8.0h
-1With hydrogen to oil volume ratio 300: 1～2500: 1.
8, method for hydrogen cracking according to claim 1 is characterized in that, described hydrocracking condition is: hydrogen dividing potential drop 3～20MPa, 280～480 ℃ of temperature, air speed 0.1～8.0h
-1, hydrogen to oil volume ratio 300: 1～2500: 1.
9, method for hydrogen cracking according to claim 1 or 5 is characterized in that described hydrocracking condition is: hydrogen dividing potential drop 4～17MPa, 300～440 ℃ of temperature, air speed 0.5～5.0h
-1, hydrogen to oil volume ratio 500: 1～2000: 1.
10, method for hydrogen cracking according to claim 1 is characterized in that, the employed Nobel metal hydrogen cracking catalyst of hydrocracking zone composed as follows:
Pd is or/and Pt 0.05wt%～2.0wt%;
Modified Y zeolite 5wt%～95wt%;
The tackiness agent surplus.
11, method for hydrogen cracking according to claim 10 is characterized in that, comprises the base metal of 0.5wt%～10wt% in the described modified Y zeolite, and its sial weight ratio is 5.5～50, and unit cell parameters is 2.430～2.455nm.
12, method for hydrogen cracking according to claim 10 is characterized in that, the specific surface area of described Nobel metal hydrogen cracking catalyst is 350～700m
2/ g, pore volume are 0.35～0.65ml/g.
13, method for hydrogen cracking according to claim 10 is characterized in that, described modified Y zeolite is to be raw material with NaY, carries out with non-noble metal water soluble salt that ion-exchange obtains.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101896579A (en) * | 2007-10-15 | 2010-11-24 | 环球油品公司 | Method for hydrogen cracking |
| CN103773482A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrocracking method used for producing high-quality chemical raw materials |
| CN104114679A (en) * | 2011-07-29 | 2014-10-22 | 沙特阿拉伯石油公司 | Hydrocracking process with interstage steam stripping |
| CN104611046A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Low energy-consumption two-stage hydrocracking method |
| CN104611025A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Low energy consumption hydrocracking method for producing high-quality chemical industry raw material |
| CN109423336A (en) * | 2017-08-31 | 2019-03-05 | 中国石油化工股份有限公司 | A kind of method for hydrogen cracking |
| CN109536205A (en) * | 2019-01-23 | 2019-03-29 | 陕西东鑫垣化工有限责任公司 | A kind of light tar mixes refining wax oil processing unit (plant) and method |
| WO2021023172A1 (en) | 2019-08-05 | 2021-02-11 | 中国石油化工股份有限公司 | Full conversion method and device for producing light aromatic hydrocarbons from catalytic diesel |
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2006
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101896579B (en) * | 2007-10-15 | 2013-04-17 | 环球油品公司 | Hydrocracking process |
| CN101896579A (en) * | 2007-10-15 | 2010-11-24 | 环球油品公司 | Method for hydrogen cracking |
| CN104114679A (en) * | 2011-07-29 | 2014-10-22 | 沙特阿拉伯石油公司 | Hydrocracking process with interstage steam stripping |
| CN103773482B (en) * | 2012-10-24 | 2015-09-02 | 中国石油化工股份有限公司 | A kind of method for hydrogen cracking producing high-quality industrial chemicals |
| CN103773482A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Hydrocracking method used for producing high-quality chemical raw materials |
| CN104611046A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Low energy-consumption two-stage hydrocracking method |
| CN104611025A (en) * | 2013-11-05 | 2015-05-13 | 中国石油化工股份有限公司 | Low energy consumption hydrocracking method for producing high-quality chemical industry raw material |
| CN104611046B (en) * | 2013-11-05 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of low energy consumption two-segment hydrocracking method |
| CN104611025B (en) * | 2013-11-05 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of low energy consumption method for hydrogen cracking producing high-quality industrial chemicals |
| CN109423336A (en) * | 2017-08-31 | 2019-03-05 | 中国石油化工股份有限公司 | A kind of method for hydrogen cracking |
| CN109423336B (en) * | 2017-08-31 | 2020-09-11 | 中国石油化工股份有限公司 | Hydrocracking method |
| CN109536205A (en) * | 2019-01-23 | 2019-03-29 | 陕西东鑫垣化工有限责任公司 | A kind of light tar mixes refining wax oil processing unit (plant) and method |
| WO2021023172A1 (en) | 2019-08-05 | 2021-02-11 | 中国石油化工股份有限公司 | Full conversion method and device for producing light aromatic hydrocarbons from catalytic diesel |
| WO2022083526A1 (en) | 2020-10-19 | 2022-04-28 | 中国石油化工股份有限公司 | Chemical hydrocracking catalyst, preparation method therefor, and application thereof |
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