CN103074103A - Combined hydrotreating method - Google Patents
Combined hydrotreating method Download PDFInfo
- Publication number
- CN103074103A CN103074103A CN2011103287387A CN201110328738A CN103074103A CN 103074103 A CN103074103 A CN 103074103A CN 2011103287387 A CN2011103287387 A CN 2011103287387A CN 201110328738 A CN201110328738 A CN 201110328738A CN 103074103 A CN103074103 A CN 103074103A
- Authority
- CN
- China
- Prior art keywords
- reaction zone
- metal component
- accordance
- oil
- hydrogenation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a combined hydrotreating method. According to the method, a wax oil raw material enters a first hydrogenation reaction zone with an up-flow manner, such that a hydrotreating reaction is carried out; a reaction effluent from the first hydrogenation reaction zone enters a thermal high pressure separator; liquid-phase material flow from the bottom of the thermal high pressure separator is further separated by a thermal low pressure separator, such that dissolved gas is separated, and the material is directly used as a feed for a catalytic cracking device; hydrogen-rich gas and hydrocarbon fraction separated from the top of the thermal high pressure separator are mixed with a fresh diesel raw material; the mixture is subjected to a hydrogenation modification reaction in a second hydrogenation reaction zone; a reaction effluent from the second hydrogenation reaction zone is separated, such that a hydrogen-rich gas is obtained; and the hydrogen-rich gas is compressed, and is circulated back to the first hydrogenation reaction zone and the second hydrogenation reaction zone. With the method provided by the invention, device equipment investment and operation cost can be effectively reduced, and oil refining process economic efficiency can be improved to a maximal extent.
Description
Technical field
The present invention relates to a kind of method made from extra care hydrocarbon ils in the presence of hydrogen, more particularly, is a kind of combined hydrogenation method of producing fcc raw material and fine-quality diesel oil.
Background technology
Along with the increase of environmental protection pressure, particularly the specification of quality of vehicle fuel is more and more higher to the refining of petroleum product in the whole society.In addition, crude resources in poor quality trend is obvious in the world wide, and the whole up-trend of crude oil price is obvious.The profit margin of Oil Refining Industry has been compressed in high quality product requirement and the increase of crude oil procurement cost, and Oil Refining Industry is wanted the essential level of crude oil processing, increase purpose product yield, the productive rate of minimizing low value by product of fully improving of survival and development.
The catalytically cracked material pre-treatment is one of a kind of technological approaches that satisfies above-mentioned challenge.Various wax oil cuts as one of main charging of catalytic cracking are carried out pre-treatment, can effectively reduce the detrimental impurity content such as SOx and NOx in the sulphur content of catalytic cracking product and nitrogen content and the catalysis flue gas, improve the yield of catalytic cracking process high-value product, reduce the agent consumption of catalytic cracking process.
US Patent No. 4780193 has been announced a kind of technology, and this technology adopts the pretreated method of hydrogenation to improve the quality of catalytically cracked material, and the hydrotreatment temperature of reaction is lower than 390 ℃, and reaction pressure is preferably in more than the 12.0MPa more than 10.0MPa.Be conducive to remove sulphur, nitrogen and aromatic hydrocarbons by hydrofining under the processing condition of aromatic saturation, improving the cracking performance of catalytic cracking unit raw material, thus improve the transformation efficiency of catalytic cracking unit, produce the high gasoline blend component of octane value.Reduce significantly catalytically cracked material sulphur and nitrogen content by hydrotreatment, thereby, can reduce significantly the content of SOx in the catalytic cracking flue gas, the cracking catalyst deactivation rate also can reduce owing to the minimizing of nitrogen content in the raw material.
Chinese patent application 200610002376.1 has disclosed a kind of grading method of wax oil hydrogenation pretreatment catalyst.Decompressed wax oil raw material inferior is processed in one or more combination and the one-pass technical process of single hop that this patented technology adopts hydrogenation protecting agent/hydrodemetallation (HDM) sweetening agent/wax oil hydrogenation to process in the catalyzer of catalyzer; can realize decompressed wax oil hydrogenating desulfurization inferior, hydrodenitrification, hydrodemetallation (HDM), be the purpose of catalytic cracking unit production high-quality charging.
But the wax oil hydrogenation preprocessing process is because the raw material boiling range is heavier, except hydrogenating desulfurization and hydrodenitrification reactive behavior reduce, also because stock oil studies on asphaltene, carbon residue, metal content is higher and so that catalyst deactivation rate increases, shorten running period.General wax oil hydrogenation treating processes must be made harsh restriction to bituminous matter, carbon residue and the metal content of raw material wax oil in order to obtain economic running period.How to guarantee when reaching the hydrogenating desulfurization of expectation, the hydrodenitrification degree of depth that be one of Major Difficulties of wax oil hydrogenation preprocessing process technological development long running period.
On the other hand, as middle preprocessing process, the pretreated application of catalytically cracked material often is subject to the restriction of Technical Economy.The economy, reduction investment and the running cost that how to improve catalytically cracked material hydrogenation preprocessing process are another focuses of technological development.Except developing high performance catalyzer, developing all kinds of COMBINED PROCESS becomes the main path that improves catalytically cracked material hydrogenation preconditioning technique level and economy.At present, refinery is in order to produce clear gusoline, and gasoline and diesel hydrogenation is refining, hydro-upgrading has obtained greatly developing.
US7763218 has disclosed a kind of combination process and equipment of hydrotreatment-mild hydrocracking.This patent can under the middle pressure of 80～140 bar, process boiling range greater than 260 ℃, asphalt content less than 0.1% all kinds of wax oil raw materials.The raw material wax oil at first enters the first hydrotreating reactor, hydrotreatment resultant stream isolate the partially liq product enter hydrotreatment/hydrocracking catalyst is housed the second reactor with the middle runnings of production high-quality.But the method production sulphur content is less than the FCC charging of 1000ppm and the middle runnings product of high-quality.
US6843906 discloses a kind of combined technical method that high-sulfur VGO produces catalytically cracked material and cracked fuel oil of processing simultaneously.Can be used for the FCC raw material of production high-quality and the diesel product of super low sulfur.Can control FCC gasoline products sulphur content less than 30 μ g/g with the hydrogenation wax oil as the FCC charging.Isolate the wax oil hydrogenation diesel oil distillate that produces and the diesel oil that other cracking unit produces and mix further hydrogenating desulfurization production ultra-low-sulphur diesel.
Chinese patent application 200510084001 has been announced the COMBINED PROCESS of a kind of VGO and catalytic cracking.The characteristics of this Technology are that catalytic diesel oil and heavy cycle oil that catalytic cracking unit is produced are all looped back VGO, are conducive to improve the quality of product yield and catalytic diesel oil.
Usually, the faulty wax oil raw material can remove sulphur, nitrogen, metal impurities after hydrotreatment, and saturated polycyclic aromatic hydrocarbons improves its cracking performance.But, when processing faulty wax oil raw material, be subject to great impact the running period of hydrotreater.In order to guarantee its running period, then need wax oil raw material key index such as asphalt content, carbon residue and metal equal size are limited more harshly.
In addition, in the wax oil hydrogenation treating processes, can produce the diesel oil distillate of a part because boiling range lightens, this part diesel oil distillate has lower sulphur content, but its cetane value is lower, generally below 45, also need further to improve its cetane value and reduce sulphur content from generating diesel by hydrotreating production high standard diesel product.The catalytic diesel oil that catalytic cracking unit is produced has high aromaticity content and low cetane value, and the catalytic diesel oil such as the MIP diesel cetane-number that especially obtain after the hydrogen transfer reactions of new catalytic cracking technique are lower.Producing clean diesel with catalytic cracking diesel oil not only needs to reduce sulphur content and also must increase substantially its cetane value.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of and can improve the hydrotreatment effect, prolong running period, reduce the hydrotreatment of investment and process cost-the hydro-upgrading combined technical method.
The present invention is directed to the above-mentioned deficiency of prior art, provide a kind of and can process simultaneously the height integrated combination processing method that faulty wax oil is produced fine quality catalytic cracking raw material and produced clean diesel with catalytic cracking diesel oil at interior various poor ignition quality fuels.Method provided by the invention arranges two hydroconversion reaction zones, a shared hydrogen gas system, and comprise the steps:
(1) the above streamed hydrotreating reactor that enters in the first hydroconversion reaction zone of wax oil raw material carries out the hydrotreatment reaction, and the reaction effluent of the first hydroconversion reaction zone enters high pressure hot separator,
(2) logistics of high pressure hot separator bottom liquid phases is after thermal low-pressure separators is further isolated dissolved gases, directly as the charging of catalytic cracking unit,
(3) the isolated hydrogen-rich gas in high pressure hot separator top and hydrocarbon fraction after fresh diesel raw material is mixed, enter the second hydroconversion reaction zone and carry out the hydro-upgrading reaction,
The reaction effluent of (4) second hydroconversion reaction zones enters cold high pressure separator and carries out gas-liquid separation, compressed the first hydroconversion reaction zone and the second hydroconversion reaction zone of looping back of separating obtained hydrogen-rich gas, the system pressure of the first hydroconversion reaction zone and the second hydroconversion reaction zone is 4.0～12.0MPa.
Since wax oil hydrogenation of the present invention process with to improve cetane value, to reduce sulphur content as main purpose diesel oil hydrogenation modification technology has identical working pressure, share same hydrogen gas system, can improve energy utilization efficiency, reduce facility investment.
The boiling spread of described wax oil raw material is 250～615 ℃, is selected from straight-run gas oil, wax tailings, catalysis heavy cycle oil, the deasphalted oil one or more.
In step (1), the wax oil raw material is with after hydrogen-rich gas mixes, at the first hydroconversion reaction zone from the streamed reactor that enters more than the hydrotreating reactor bottom that is filled with the combined hydrogenation catalyzer.So that the hydrotreating reactor inner catalyst is in the microdilatancy state, can increase bed voidage, delay the bed pressure drop climbing speed and then prolong running period, improve stock oil adaptability.In wax oil hydrogenation was processed up-flow reactor, wax oil raw material and hydrogen carried out the reactions such as hydrogenating desulfurization, hydrodenitrification, aromatic hydrogenation are saturated, hydrodemetallation (HDM) under catalyst action.
The asphalt content of upflowing hydrotreating reactor fresh feed wax oil should not be preferably in below the 1000 μ g/g greater than 2000 μ g/g, and carbon residue should be greater than 2%, and preferably less than 1%, total metal contents in soil is not more than 10 μ g/g, and is the most desirable below 2 μ g/g.Than prior art, wax oil raw material properties limit value has to a certain degree and relaxes.
The hydrotreatment reaction conditions of the first hydroconversion reaction zone is: 300～430 ℃ of average bed temperatures, hydrogen-oil ratio 300～1000Nm
3/ m
3, volume space velocity 0.5～3.0h
-1
Described the first hydroconversion reaction zone; load successively wax oil hydrogenation protective material, demetalization sweetening agent, hydrotreating catalyst according to the flow direction of reactant flow, take the first hydroconversion reaction zone integer catalyzer as benchmark, its admission space mark is followed successively by 2%～10%; 1%～30%, 68%～95%.
Described wax oil hydrogenation is protectant to be consisted of: the alumina supporter of 0.5～5.0 heavy % nickel oxide, 2.0～10.0 heavy % molybdenum oxides and surplus.The wax oil hydrogenation protective material that preferred described wax oil hydrogenation protective material is two kinds of grading loadings, adopting two kinds of protectant purposes is in order to form active gradient, to be conducive to reduce beds pressure drop climbing speed, improving running period.
Described demetalization sweetening agent contains a kind of macropore alumina supporter and the molybdenum and/or tungsten and nickel and/or the cobalt metal component that load on this carrier, wherein said alumina supporter can several apertures be 5～20nm, pore volume is greater than 0.6～1.2ml/g, and specific surface area is 80～400m
2/ g, the metal component of demetalization sweetening agent is: molybdenum oxide and/or Tungsten oxide 99.999 5～40 heavy %, nickel oxide and/or cobalt oxide 1～10 heavy %.The metal component of preferred demetalization desulfurization catalyst is cobalt oxide and molybdenum oxide.
Described hydrotreating catalyst can be the hydrotreating catalyst of loading type and/or the hydrotreating catalyst of non-loading type.
It is a kind of fluorine-containing, phosphorus hydrogenation catalyst take silica-alumina as carrier that described load hydrogenation is processed catalyzer, take this catalyzer integral body as benchmark, it consists of: nickel oxide 1～10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, fluorine 1～10 % by weight, phosphorus oxide 0.5～8 % by weight, surplus are silica-alumina.
In order to reach better hydrotreatment effect, except adopting the hydrotreating catalyst of loading type, hydrotreating catalyst that also can non-loading type replaces part or all of hydrotreating catalyst.
Described non-supported hydrogenation is processed catalyzer and is contained at least a VIII family metal component, at least two kinds of group vib metal components and organic additive, and the content of a kind of VIII family metal component, at least two kinds of group vib metal components and organic additive satisfies: mR:[VIII
x(VIB-1)
y(VIB-2)
z] O
2Wherein, represent a kind of group vib metal component VIB-2 with VIB-1 and represent another kind of group vib metal component; R represents at least a organic additive; M represents every mole of [VIII
x(VIB-1)
y(VIB-2)
z] O
2In the mole number of contained organic additive, the span of m is 0.1～2, take the total amount of VIII family metal component, VIB-1 metal component and VIB-2 metal component as benchmark; X, y, z represent respectively VIII family metal component, the VIB-1 metal component, and the molar fraction of VIB-2 metal component, x, y, the span of z satisfies (y+z): x=10: 1～1: 10.
Described group VIII metal component is cobalt, nickel and composition thereof, and described group vib metal component is molybdenum and tungsten; Preferred described x, y, the span of z satisfies (y+z): x=3: 1～1: 3, and y: z=3: 1～1: 3.
Described organic additive is selected from the organic ammonium compound, one or more in sulfonate and the organophosphate.Described organic ammonium compound is selected from one or more in tetraethylammonium bromide, tetraethyl ammonium hydroxide, 4-propyl bromide, TPAOH, hexamethylenetetramine, the Dodecyl trimethyl ammonium chloride; Sulfonate is selected from sodium laurylsulfonate and/or Sodium dodecylbenzene sulfonate.Non-supported hydrogenation is processed in the catalyzer and is also contained binding agent, and take hydrotreating catalyst as benchmark, the content of described binding agent is no more than 75 % by weight.Preferred described binding agent is aluminum oxide, silicon oxide, silica-alumina, and take hydrotreating catalyst as benchmark, the content of described binding agent is no more than 30 % by weight.
The resultant of up-flow reactor flows in the high pressure hot separator with separation function, and the service temperature of described high pressure hot separator is 150～350 ℃.
In step (2), the logistics of high pressure hot separator bottom liquid phases after thermal low-pressure separators is further isolated dissolved gases, needn't be again through fractionation can be directly as the high-quality charging of catalytic cracking unit, to reduce investment outlay and process cost.
In step (3), the isolated hydrogen-rich gas in high pressure hot separator top and hydrocarbon fraction, it is the following cut of diesel oil that the hydrotreatment reaction generates, in order to take full advantage of its pressure energy, after the fresh diesel raw material of among the present invention itself and another feed system being sent here is mixed, enter the second hydroconversion reaction zone and carry out the hydro-upgrading reaction, advance one one and improve its cetane value, reduction sulphur content.
The boiling spread of fresh feed diesel raw material is 190～400 ℃, is selected from catalytic diesel oil, coker gas oil, straight-run diesel oil, visbreaking diesel oil, the gelatin liquefaction diesel oil one or more.Sulphur content is preferably in below the 25000 μ g/g, and nitrogen content is preferably in below the 1500 μ g/g.
The reaction conditions of the second hydroconversion reaction zone is: 300～400 ℃ of average bed temperatures, hydrogen-oil ratio 300～1200Nm
3/ m
3, volume space velocity 0.4～2.0h
-1
Described the second hydroconversion reaction zone loads hydrofining agent and hydro-upgrading agent successively according to the flow direction of reactant flow, and the admission space ratio of hydrofining agent and hydro-upgrading agent is 30%～75% and 25%～70%.
The diesel oil hydrogenation protective material that accounts for hydrofining agent volume 5%～10% can be loaded in the Hydrobon catalyst upstream, the back end hydrogenation catalyst for refining that accounts for hydro-upgrading agent volume 10%～20% can be loaded in the catalyst for hydro-upgrading downstream.
Described diesel oil hydrogenation protective material is VIB or VIII family non-precious metal catalyst or their combination that loads on unformed aluminum oxide and/or the silica-alumina supports.This type of protective material has larger pore volume and specific surface area.Preferably diesel oil hydrogenation is protectant consists of: take the catalyzer total amount as benchmark, and in oxide compound, nickel oxide 1.0～5.0 heavy %, molybdenum oxide 5.5～10.0 heavy %, surplus is alumina supporter.
Described hydrofining agent is fluorine-containing, phosphorus hydrogenation catalyst take silica-alumina as carrier, consisting of after this catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, fluorine 1-10 % by weight, phosphorus oxide 0.5-8 % by weight, surplus are silica-alumina.
Described hydro-upgrading agent is by a kind of carrier and load on group VIII metal component on this carrier and the metal component of group vib forms, and described carrier is comprised of aluminum oxide, amorphous aluminum silicide (or partially-crystallized amorphous aluminum silicide) and zeolite.
The preferred described hydro-upgrading agent of the present invention, take catalyzer as benchmark, the silica-alumina that contains 1～70 heavy %, the y-type zeolite of 1～60 heavy %, the aluminum oxide of 5～80 heavy % in oxide compound, contains the group VIII metal component of 1～15 heavy %, the metal component of the group vib of 10～40 heavy %, described silica-alumina has structure of similar to thin diaspore.
Described silica-alumina with structure of similar to thin diaspore, preferred N value is 0.1～1, also has the silicon oxide of 5～60 heavy % after the roasting, the aluminum oxide of 40～95 weight %, N=P1/P2 wherein, P1 is the solid of described silica-alumina
27Chemical shift is the peak area at 60 ± 0.1-0.2ppm place in the Al NMR spectrogram, and P2 is the solid of described silica-alumina
27Chemical shift is the peak area at 5 ± 0.1-0.2ppm place in the Al NMR spectrogram.
27Each peak area of chemical shiftsum at each peak is measured take saturated alum liquor as reference on Varian UnityInova 300M type nuclear magnetic resonance spectrometer in the Al NMR spectrogram.Described y-type zeolite can be common y-type zeolite, ultrastable Y－type zeolite, phosphorous ultrastable Y－type zeolite or rare earth Y type zeolite.The preferred gama-alumina of described aluminum oxide and contain that one or more are selected among titanium, magnesium, boron, zirconium, thorium, niobium, the rare earth one or more add the gama-alumina of components.
Described aluminum oxide by little porous aluminum oxide and macroporous aluminium oxide according to 75: 25-25: 75 weight ratio is composited, wherein, to be diameter account for the aluminum oxide of total pore volume more than 95% less than the pore volume in 80 dust holes to little porous aluminum oxide, and macroporous aluminium oxide is that the pore volume in diameter 60-600 dust hole accounts for the aluminum oxide of total pore volume more than 70%.
In step (4), the reaction effluent of the second hydroconversion reaction zone enters cold high pressure separator and carries out gas-liquid separation, compressed the first hydroconversion reaction zone and the second hydroconversion reaction zone of looping back of separating obtained hydrogen-rich gas, the system pressure of the first hydroconversion reaction zone and the second hydroconversion reaction zone is 4.0～12.0MPa.The second hydroconversion reaction zone resultant flow through high score, separated the liquid whole product introduction fractionating system that obtains in low minute and obtain the purpose products such as petroleum naphtha and diesel oil.
The present invention has following advantage:
1. adopt high performance hydrotreating catalyst combination and up-flow reactor, can improve hydrogenating desulfurization, hydrodenitrification and the aromatic hydrogenation saturation effect of faulty wax oil, delay as far as possible the bed pressure drop rising degree of depth simultaneously, increase running period.
2. faulty wax oil hydrotreatment, the diesel oil hydrogenation modification process that working pressure is similar carried out the organic integration combination, two hydroconversion reaction zones share hydrogen gas compressor, improved the utilising efficiency of recycle hydrogen, reduced total hydrogen-oil ratio and energy consumption, favourable reduction appliance arrangement investment and process cost; The diesel oil that wax oil hydrogenation processing reaction process generates, petroleum naphtha etc. enter the diesel modifying reaction zone than light constituent, can further improve its quality, have shared simultaneously fractionating system, also are conducive to reduce investment and process cost.
3. the hydrotreatment reaction generates oil after hot high score, heat were separated in low minute, and liquid phase stream avoids wax oil to enter fractionation plant directly as the catalytic cracking unit charging, can reduce the load of separation column, thereby reduces energy consumption and process cost;
4. the good quality of product that obtains of the present invention, it is low that wax oil hydrogenation is processed the wax oil sulphur nitrogen content that obtains, the diesel oil distillate that the wax oil hydrogenation processing reaction produces and poor ignition quality fuel raw material can obtain the clean diesel product through hydro-upgrading, and foreign matter content is low and cetane value is high.
Description of drawings
Accompanying drawing is built-up type hydroprocessing process schematic flow sheet provided by the invention.
Embodiment
Below in conjunction with accompanying drawing method of the present invention is illustrated further, but not thereby limiting the invention.As shown in the figure:
From the faulty wax oil raw material of pipeline 1 after interchanger 3 and interchanger 4 heat exchange, after hydrogen mixes, after process furnace 5 heating, through pipeline streamed hydrotreating reactor 7 that enters more than 6, carry out the hydrotreatment reaction, its reaction effluent enters high pressure hot separator 10 through pipeline 9 after pipeline 8 enters interchanger 4 heat exchange.High pressure hot separator 10 bottom liquid phases logistics are after pipeline 12 enters thermal low-pressure separators 13 and further isolates dissolved gases 14, and its liquid phase stream is through pipeline 15 withdrawing devices, directly as the charging of catalytic cracking unit,
From the fresh poor ignition quality fuel raw material of pipeline 2 with mix from the new hydrogen of pipeline 16 with from the circulating hydrogen of pipeline 23 after, after process furnace 5 heating, through pipeline 17 with mix from the isolated hydrogen-rich gas in high pressure hot separator 10 tops of pipeline 11 and hydrocarbon fraction after, enter the second hydroconversion reaction zone 18 and carry out the hydro-upgrading reaction.The reaction effluent of the second hydroconversion reaction zone is after interchanger 3 heat exchange, enter cold high pressure separator 19 and carry out gas-liquid separation, separating obtained hydrogen-rich gas through pipeline 20 after 21 desulfurization of desulphurization of recycle hydrogen tank, after entering circulating hydrogen compressor 22 and boosting, loop back the first hydroconversion reaction zone and the second hydroconversion reaction zone through pipeline 23.Cold high pressure separator 19 separating obtained liquid phase streams enter cold low separator 25 through pipeline 24 and carry out further gas-liquid separation.The gas that separates is discharged through pipeline 26, and the liquid phase stream of separation enters separation column 28 through pipeline 27.Gas, petroleum naphtha and the diesel product of separation column 28 fractionation gained discharged through pipeline 29,30 and 31 respectively.
The following examples will be further described method provided by the invention, but not thereby limiting the invention.
Implement method of the present invention at the 250ml testing apparatus that is provided with as shown in drawings upflow fixed bed hydrotreating reactor and conventional fixed bed hydrogenation reforming reactor.The faulty wax oil raw material is the mixing oil of high-sulfur decompressed wax oil and wax tailings among the embodiment, and its character is listed in table 1.Fresh diesel raw material is for urging straight bavin mixing oil, and character is listed in table 2.The first hydroconversion reaction zone loads the catalyst combination that the commercial trade mark is respectively RG-10A/RG-10B/RMS-1/RN-32V successively according to the flow direction of reactant flow, and the admission space ratio is 5: 5: 20: 70.The second hydroconversion reaction zone loads the catalyst combination that the commercial trade mark is RG-1/RS-1000/RIC-2/RS-1000 successively according to the flow direction of reactant flow, and the admission space ratio is 10: 65: 35: 10.The reaction conditions of the first reaction zone and second reaction zone is listed in table 3.Host volume space velocity in the table 4 described in the first hydroconversion reaction zone refers to not comprise the volume space velocity of wax oil hydrogenation protective material (RG-10A/RG-10B).
The reaction effluent of the first hydroconversion reaction zone enters high pressure hot separator, thermal low-pressure separators, obtains refining wax oil, and the reaction effluent of the second hydroconversion reaction zone obtains diesel product after entering cold high pressure separator, cold low separator and separation column.Products obtained therefrom character is listed in table 3.
As can be seen from Table 3, the carbon residue content of refining wax oil is＜0.3 % by weight, and sulphur content is 950 μ g/g, is the catalytically cracked material of high-quality.The cetane value of diesel product has improved 26 units, is 52.3, and sulphur content＜10 μ g/g satisfies the requirement of Europe V diesel oil standard.
Table 1 wax oil feedstock property
| The stock oil title | Deep drawing wax oil inferior and wax tailings mixing oil |
| Density g/cm 3 | 0.9365 |
| Refractive power n D 70 | 1.5088 |
| C ％ | 86.18 |
| H ％ | 11.74 |
| S μg/g | 18300 |
| N μg/g | 2500 |
| Bituminous matter, μ g/g | 1500 |
| Carbon residue, % | 1.2 |
| Total metal, μ g/g | 3.0 |
| Boiling range (D-1160) ℃ | |
| Initial boiling point | 258 |
| 10％ | 409 |
| 50％ | 461 |
| 90％ | 526 |
| Whole gold-plating point | 565 |
Table 2 raw material diesel oil character
| Project | Urge straight bavin mixing oil |
| Density (20 ℃), g/cm 3 | 0.9067 |
| Sulphur content, μ g/g | 6300 |
| Nitrogen content, μ g/g | 712 |
| Cetane value | 26.2 |
| Boiling range, ℃ | |
| Initial boiling point | 196 |
| 10％ | 227 |
| 50％ | 273 |
| 90％ | 336 |
| Final boiling point | 363 |
Table 3 processing parameter and product property
Claims (18)
1. a built-up type hydroprocessing process is characterized in that, two hydroconversion reaction zones are set, a shared hydrogen gas system, and comprise the steps:
(1) carry out the hydrotreatment reaction in the above streamed hydrogenator that enters the first hydroconversion reaction zone of wax oil raw material, the reaction effluent of the first hydroconversion reaction zone enters high pressure hot separator,
(2) logistics of high pressure hot separator bottom liquid phases is after thermal low-pressure separators is further isolated dissolved gases, directly as the charging of catalytic cracking unit,
(3) the isolated hydrogen-rich gas in high pressure hot separator top and hydrocarbon fraction after fresh diesel raw material is mixed, enter the second hydroconversion reaction zone and carry out the hydro-upgrading reaction,
The reaction effluent of (4) second hydroconversion reaction zones enters cold high pressure separator and carries out gas-liquid separation, compressed the first hydroconversion reaction zone and the second hydroconversion reaction zone of looping back of separating obtained hydrogen-rich gas, the system pressure of the first hydroconversion reaction zone and the second hydroconversion reaction zone is 4.0～12.0MPa.
2. in accordance with the method for claim 1, it is characterized in that the boiling spread of described wax oil raw material is 250～615 ℃, be selected from straight-run gas oil, wax tailings, catalysis heavy cycle oil, the deasphalted oil one or more.
3. in accordance with the method for claim 1, it is characterized in that the hydrotreatment reaction conditions of the first hydroconversion reaction zone is: 300～430 ℃ of average bed temperatures, hydrogen-oil ratio 300～1000Nm
3/ m
3, volume space velocity 0.5～3.0h
-1The service temperature of described high pressure hot separator is 150～350 ℃.
4. in accordance with the method for claim 1; it is characterized in that; described the first hydroconversion reaction zone; load successively wax oil hydrogenation protective material, demetalization sweetening agent, hydrotreating catalyst according to the flow direction of reactant flow; take the first hydroconversion reaction zone integer catalyzer as benchmark; its admission space mark is followed successively by 2%～10%, and 1%～30%, 68%～95%.
5. in accordance with the method for claim 4, it is characterized in that described wax oil hydrogenation is protectant to be consisted of: the alumina supporter of 0.5～5.0 heavy % nickel oxide, 2.0～10.0 heavy % molybdenum oxides and surplus.
6. in accordance with the method for claim 4, it is characterized in that, described demetalization sweetening agent contains a kind of macropore alumina supporter and the molybdenum and/or tungsten and nickel and/or the cobalt metal component that load on this carrier, wherein said alumina supporter can several apertures be 5～20nm, pore volume is greater than 0.6～1.2ml/g, and specific surface area is 80～400m
2/ g, the metal component of demetalization sweetening agent is: molybdenum oxide and/or Tungsten oxide 99.999 5～40 heavy %, nickel oxide and/or cobalt oxide 1～10 heavy %.
7. in accordance with the method for claim 4, it is characterized in that described hydrotreating catalyst is that load hydrogenation is processed catalyzer and/or non-supported hydrogenation is processed catalyzer.
8. in accordance with the method for claim 7, it is characterized in that, it is a kind of fluorine-containing, phosphorus hydrogenation catalyst take silica-alumina as carrier that described load hydrogenation is processed catalyzer, take this catalyzer integral body as benchmark, it consists of: nickel oxide 1～10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum be greater than 10 to 50 % by weight, fluorine 1～10 % by weight, phosphorus oxide 0.5～8 % by weight, surplus are silica-alumina.
9. in accordance with the method for claim 7, it is characterized in that, described non-supported hydrogenation is processed catalyzer and is contained at least a VIII family metal component, at least two kinds of group vib metal components and organic additive, and the content of a kind of VIII family metal component, at least two kinds of group vib metal components and organic additive satisfies: mR:[VIII
x(VIB-1)
y(VIB-2)
z] O
2Wherein, represent a kind of group vib metal component VIB-2 with VIB-1 and represent another kind of group vib metal component; R represents at least a organic additive; M represents every mole of [VIII
x(VIB-1)
y(VIB-2)
z] O
2In the mole number of contained organic additive, the span of m is 0.1～2, take the total amount of VIII family metal component, VIB-1 metal component and VIB-2 metal component as benchmark; X, y, z represent respectively VIII family metal component, the VIB-1 metal component, and the molar fraction of VIB-2 metal component, x, y, the span of z satisfies (y+z): x=10: 1～1: 10.
10. in accordance with the method for claim 9, it is characterized in that described group VIII metal component is cobalt, nickel and composition thereof, described group vib metal component is molybdenum and tungsten; Described x, y, the span of z satisfies (y+z): x=3: 1～1: 3, and y: z=3: 1～1: 3.
11. in accordance with the method for claim 9, it is characterized in that described organic additive is selected from the organic ammonium compound, one or more in sulfonate and the phosphoric acid salt.
12. in accordance with the method for claim 1, it is characterized in that the boiling spread of described diesel raw material is 190～400 ℃, be selected from catalytic diesel oil, coker gas oil, straight-run diesel oil, visbreaking diesel oil, the gelatin liquefaction diesel oil one or more.
13. in accordance with the method for claim 1, it is characterized in that the reaction conditions of the second hydroconversion reaction zone is: 300～400 ℃ of average bed temperatures, hydrogen-oil ratio 300～1200Nm
3/ m
3, volume space velocity 0.4～2.0h
-1
14. in accordance with the method for claim 1, it is characterized in that, described the second hydroconversion reaction zone loads hydrofining agent and hydro-upgrading agent successively according to the flow direction of reactant flow, and the admission space ratio of hydrofining agent and hydro-upgrading agent is 30%～75% and 25%～70%.
15. in accordance with the method for claim 1; it is characterized in that; described the second hydroconversion reaction zone; the diesel oil hydrogenation protective material that accounts for hydrofining agent volume 5%～10% can be loaded in the Hydrobon catalyst upstream, the back end hydrogenation catalyst for refining that accounts for hydro-upgrading agent volume 10%～20% can be loaded in the catalyst for hydro-upgrading downstream.
16. in accordance with the method for claim 14, it is characterized in that, described hydrofining agent is fluorine-containing, phosphorus hydrogenation catalyst take silica-alumina as carrier, consisting of after this catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, fluorine 1-10 % by weight, phosphorus oxide 0.5-8 % by weight, surplus are silica-alumina.
17. in accordance with the method for claim 14, it is characterized in that, described hydro-upgrading agent is comprised of a kind of carrier and the group VIII metal component and the group vib metal component that load on this carrier, and described carrier is comprised of aluminum oxide, amorphous aluminum silicide and zeolite.
18. in accordance with the method for claim 17, it is characterized in that, consisting of of described hydro-upgrading agent: take the hydro-upgrading agent as benchmark, silica-alumina 1～70 heavy %, y-type zeolite 1～60 heavy %, aluminum oxide 5～80 heavy %, in oxide compound, metal component 10～40 heavy % of group VIII metal component 1～15 heavy %, group vib.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103287387A CN103074103A (en) | 2011-10-26 | 2011-10-26 | Combined hydrotreating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103287387A CN103074103A (en) | 2011-10-26 | 2011-10-26 | Combined hydrotreating method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103074103A true CN103074103A (en) | 2013-05-01 |
Family
ID=48150805
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011103287387A Pending CN103074103A (en) | 2011-10-26 | 2011-10-26 | Combined hydrotreating method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103074103A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104232154A (en) * | 2013-06-21 | 2014-12-24 | 中国石油天然气股份有限公司 | Distillate oil hydrogenation modification method |
| CN104531212A (en) * | 2014-12-05 | 2015-04-22 | 何巨堂 | High aromatic hydrocarbon hydrogenation upgrading method by utilizing refined diesel component hydrogenation upgrading reaction process |
| CN104629798A (en) * | 2015-02-06 | 2015-05-20 | 北京中科诚毅科技发展有限公司 | Oil and coal hybrid hydrogenation refining technique and equipment |
| CN105524653A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Hydrotreatment method for residual oil |
| CN106731527A (en) * | 2016-12-12 | 2017-05-31 | 浙江大学 | The denitrogenation method and device of refinery hydrogen stream stock |
| CN110655949A (en) * | 2018-06-29 | 2020-01-07 | 中国石油化工股份有限公司 | Hydrogenation method of jet fuel rich in hydrogen |
| CN114133957A (en) * | 2021-11-10 | 2022-03-04 | 中国石油化工股份有限公司 | Catalytic diesel oil hydrogenation modification system and modification method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092573A (en) * | 2006-06-22 | 2007-12-26 | 中国石油化工股份有限公司 | A hydrogenation method for producing diesel oil in low sulphur |
| CN101306374A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Hydrogenation catalyst composition, preparation method and use thereof |
| CN101412923A (en) * | 2007-10-18 | 2009-04-22 | 中国石油化工股份有限公司 | Hydro-upgrading combined method |
| CN101412928A (en) * | 2007-10-18 | 2009-04-22 | 中国石油化工股份有限公司 | Hydro-desulphurizing combined method |
| CN101412926A (en) * | 2007-10-18 | 2009-04-22 | 中国石油化工股份有限公司 | Hydro-upgrading combined method |
| CN101632911A (en) * | 2008-07-24 | 2010-01-27 | 中国石油化工股份有限公司 | Up-flow reactor and application thereof |
| CN101684417A (en) * | 2008-09-27 | 2010-03-31 | 中国石油化工股份有限公司 | Optimized hydrogenation-catalytic cracking combination process |
| CN101928601A (en) * | 2009-06-25 | 2010-12-29 | 中国石油化工股份有限公司 | Processing method for catalytic cracking heavy oil |
| CN101987967A (en) * | 2009-07-30 | 2011-03-23 | 中国石油化工股份有限公司石油化工科学研究院 | Hydrotreatment method of deep vacuum distillation wax oil |
-
2011
- 2011-10-26 CN CN2011103287387A patent/CN103074103A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092573A (en) * | 2006-06-22 | 2007-12-26 | 中国石油化工股份有限公司 | A hydrogenation method for producing diesel oil in low sulphur |
| CN101306374A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Hydrogenation catalyst composition, preparation method and use thereof |
| CN101412923A (en) * | 2007-10-18 | 2009-04-22 | 中国石油化工股份有限公司 | Hydro-upgrading combined method |
| CN101412928A (en) * | 2007-10-18 | 2009-04-22 | 中国石油化工股份有限公司 | Hydro-desulphurizing combined method |
| CN101412926A (en) * | 2007-10-18 | 2009-04-22 | 中国石油化工股份有限公司 | Hydro-upgrading combined method |
| CN101632911A (en) * | 2008-07-24 | 2010-01-27 | 中国石油化工股份有限公司 | Up-flow reactor and application thereof |
| CN101684417A (en) * | 2008-09-27 | 2010-03-31 | 中国石油化工股份有限公司 | Optimized hydrogenation-catalytic cracking combination process |
| CN101928601A (en) * | 2009-06-25 | 2010-12-29 | 中国石油化工股份有限公司 | Processing method for catalytic cracking heavy oil |
| CN101987967A (en) * | 2009-07-30 | 2011-03-23 | 中国石油化工股份有限公司石油化工科学研究院 | Hydrotreatment method of deep vacuum distillation wax oil |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104232154A (en) * | 2013-06-21 | 2014-12-24 | 中国石油天然气股份有限公司 | Distillate oil hydrogenation modification method |
| CN104232154B (en) * | 2013-06-21 | 2016-04-06 | 中国石油天然气股份有限公司 | Distillate oil hydrogenation modification method |
| CN105524653A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Hydrotreatment method for residual oil |
| CN105524653B (en) * | 2014-09-29 | 2017-05-24 | 中国石油化工股份有限公司 | Hydrotreatment method for residual oil |
| CN104531212A (en) * | 2014-12-05 | 2015-04-22 | 何巨堂 | High aromatic hydrocarbon hydrogenation upgrading method by utilizing refined diesel component hydrogenation upgrading reaction process |
| CN104629798A (en) * | 2015-02-06 | 2015-05-20 | 北京中科诚毅科技发展有限公司 | Oil and coal hybrid hydrogenation refining technique and equipment |
| WO2016124148A1 (en) * | 2015-02-06 | 2016-08-11 | 北京中科诚毅科技发展有限公司 | Coal and oil hybrid hydrogenation refining technique and device |
| US10344238B2 (en) | 2015-02-06 | 2019-07-09 | Catech Technology Co., Ltd. | Coal and oil co-hydrotreating processing technology and equipment |
| CN106731527A (en) * | 2016-12-12 | 2017-05-31 | 浙江大学 | The denitrogenation method and device of refinery hydrogen stream stock |
| CN110655949A (en) * | 2018-06-29 | 2020-01-07 | 中国石油化工股份有限公司 | Hydrogenation method of jet fuel rich in hydrogen |
| CN110655949B (en) * | 2018-06-29 | 2021-10-08 | 中国石油化工股份有限公司 | Hydrogenation method of jet fuel rich in hydrogen |
| CN114133957A (en) * | 2021-11-10 | 2022-03-04 | 中国石油化工股份有限公司 | Catalytic diesel oil hydrogenation modification system and modification method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101684417B (en) | Optimized hydrogenation-catalytic cracking combination process | |
| US20080230441A1 (en) | Hydrotreating And Hydrocracking Process And Apparatus | |
| CN103074103A (en) | Combined hydrotreating method | |
| CN102051217B (en) | Hydrogenation method for producing ultra-low sulfur clean diesel | |
| CN102453535B (en) | Hydrocracking method for reforming material yield increase | |
| CN100587038C (en) | Hydrogenation method for producing good quality catalytic cracking material | |
| CN103059972A (en) | Combined hydrogenation method of producing chemical materials | |
| CN103059986A (en) | Hydrocracking method for producing chemical materials | |
| CN104560188B (en) | A kind of combined hydrogenation method of voluminous gasoline | |
| CN101987967B (en) | Hydrotreatment method of deep vacuum distillation wax oil | |
| CN102344826B (en) | Combined hydrogenation method for producing catalytic raw material and high-quality diesel oil | |
| CN103773462B (en) | A kind of two-segment hydrocracking method producing high-quality industrial chemicals | |
| CN103059990B (en) | Efficient catalytic conversion method for petroleum hydrocarbon | |
| CN102911730B (en) | Catalytic conversion method for high sulfur wax oil | |
| CN102807898B (en) | Hydrocracking method for increasing production of high-quality middle distillates | |
| CN102719272B (en) | A kind of catalysis conversion method of petroleum hydrocarbon | |
| CN103059993B (en) | Catalytic conversion method of petroleum hydrocarbon | |
| CN100575459C (en) | The hydroprocessing process of Fisher-Tropsch synthesis fuels | |
| CN101177627A (en) | Hydrogenation processing method for f-t synthetic oil | |
| CN102807896B (en) | Hydrotreating method for maximum production of middle distillates | |
| CN113122319B (en) | Hydrocracking process for producing high-quality reforming raw material | |
| CN102453536A (en) | Integrated hydrogenation method for producing clean diesel | |
| CN101177620A (en) | Hydrogenation processing method for f-t synthetic oil | |
| CN102911732B (en) | Catalytic conversion method of high-sulfur wax oil | |
| CN101177628A (en) | Hydrogenation processing method for f-t synthetic oil full range |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130501 |