CN103789033A - Method for hydro-upgrading of heavy benzene to produce clean fuel oil - Google Patents
Method for hydro-upgrading of heavy benzene to produce clean fuel oil Download PDFInfo
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Abstract
The invention discloses a method for hydro-upgrading of heavy benzene to produce clean fuel oil. The method includes: subjecting heavy benzene to pre-hydrofining and main hydrofining, then conducting gas-liquid separation by a hot high pressure separator and a hot low pressure separator, cycling part of the obtained hot low distillate oil back to a main hydrogenation reaction area, leading the rest part of hot low distillate oil into a hydro-upgrading reaction area, mixing the hydro-upgrading product with the gas separated by the hot high pressure separator and bringing the mixture into a cold high pressure separator, making the gas separated by the hot low pressure separator and the liquid phase separated by the cold high pressure separator enter a cold low pressure separator, subjecting the separated liquid to stripping by a stripping tower and then leading the liquid from the stripping tower into a fractionating tower, thus obtaining gasoline and diesel fractions. The method provided by the invention can greatly reduce the temperature rise of equipment, extend the equipment operation cycle, reduce the load of a circulating hydrogen compressor, and save equipment investment, thus providing a high economical processing method for heavy benzene with low added value. The method not only develops new application of the raw material, but also expands the raw material sources of clean fuel oil, and increases the cetane number of diesel.
Description
Technical field
The present invention relates to a kind of method of hydrotreating of heavy benzol, particularly a kind of two-stage hydrogenation is produced the method for clean fuel oil.
Background technology
The scarcity day by day of world petroleum resource, making various non-conventional oil resources processings produce clean fuel oil tech becomes focus, and wherein one of technology is take Coal Chemical Industry by-product as producing clean fuel oil.
Heavy benzol is the by product producing in Coal Chemical Industry industry crude benzole hydrogenation process for refining process, in crude benzole hydrogenation technological process, raw material crude benzol separates in multi-stage evaporation device, high boiling component is discharged from multi-stage evaporation device bottom as Residual oil as trimethylbenzene, naphthalene, indane, coumarone etc., and this part Residual oil is heavy benzol.
Heavy benzol character is generally: 95～130 ℃ of initial boiling points, do 230～280 ℃, 20 ℃ of density 0.96～0.99g/cm
3, aromaticity content is generally 60wt%～85wt%, and unsaturated compound content is generally 18wt%～25wt%, and sulphur content is 0.9wt%～1.3wt%, and nitrogen content is 0.6wt%～1.3wt%, oxygen level is 1.0wt%～2.0wt%.Although heavy benzol boiling range is lighter, its aromaticity content is high and typical compound content concentrated, and density is large, and foreign matter content is high, therefore heavy benzol is a kind of special material that is different from petroleum fractions.
At present most domestic producer is all using heavy benzol as raw fuel stock or solvent oil processing, only has only a few enterprise for the production of coumarone-indene resin, because petroleum resin are more competitive than coumarone indene resin at the aspect such as price and performance, and coumarone indene resin is poisonous, is progressively replaced by petroleum resin.In addition, owing to containing the heterogeneous ring compounds such as a certain amount of O, S, N in heavy benzol, except stability is poor, also there is irritating smell as solvent oil, the not high and contaminate environment of quality not only during directly as oil fuel, all there is poor product quality, lack competitiveness or the problem of contaminate environment in these purposes at present.
In order to utilize better heavy benzol, improve its added value, CN101712888A discloses a kind of heavy benzene hydrogenation refining technique, the method mainly adopts fixed bed pre-hydrofining reaction district and the main hydrogenator of fixed bed to carry out selective hydrogenation refining, and the hydrogenated oil of gained obtains solvent oil and NAPTHALENE FLAKES. (INDUSTRIAL GRADE） through processes such as cooling, air lift, distillation and rectifying.The method has been improved quality product, improve to a certain extent the added value of raw material, but the hydrofining technology condition that it provides can not make heavy benzol be converted into clean fuel oil production, simultaneously for because of unsaturated component concentration in heavy benzol high, typical compound content is concentrated, the large problem of pre-hydrofining reaction district's temperature rise causing is not mentioned solution, because unsaturated compound is as higher in styrene content in heavy benzol, if there is a vinylbenzene molecule to carry out pre-hydrofining reaction, in heavy benzol, other becomes ten thousand more than one hundred million vinylbenzene molecules all will react so, consequent reaction heat will be very large, if do not take corresponding method, even liquid hydrogen injection, also may cause reducing temperature rise because choosing applicable circulating hydrogen compressor, finally cause device temperature runaway, make the permanent inactivation of catalyzer, even burn out reactor, consequence is serious, be that the method industrial implementation is poor.
Summary of the invention
In order to overcome deficiency of the prior art, the invention provides a kind of method of heavy benzene hydrogenation upgrading production clean fuel oil.The present invention not only can make heavy benzol produce clean gasoline and diesel product through hydrogenation reaction; and can effectively solve the problem that the temperature rise of hydrofining reaction district is large; the activity stability of protection catalyst for hydro-upgrading, favourable to safety and steady operation and the prolong operating period of device.
A kind of heavy benzene hydrogenation upgrading of the present invention is produced clean fuel oil method, and described method comprises:
(1) raw material heavy benzol after filtration, enters pre-hydrofining reaction district with hydrogen after mixing, and contacts carry out hydrofining reaction with Hydrobon catalyst;
(2) the pre-hydrofining products therefrom in step (1) carries out gas-liquid separation through gas-liquid separator, gained liquid product enters main hydroconversion reaction zone, pass through successively hydrogenation protecting reaction zone and main hydrofining reaction district, under hydrogen exists, contact and carry out hydrogenation reaction with Hydrobon catalyst with hydrogenation protecting catalyst successively, obtain hydrotreated product;
(3) hydrotreated product in step (2) carries out gas-liquid separation through high pressure hot separator;
(4) liquid product that in step (3), high pressure hot separator separates enters the further gas-liquid separation of thermal low-pressure separators, and low point of oil part of separating obtained heat loops back main hydroconversion reaction zone;
(5) in step (4), low point of oil of remainder heat enters hydro-upgrading reaction zone, under hydrogen exists, after catalyst for hydro-upgrading contact reacts, obtains hydro-upgrading product;
(6) in step (5) hydro-upgrading product with enter cold high pressure separator from the isolated gas of high pressure hot separator;
(7) liquid that in step (6), cold high pressure separator is separated enters cold low separator with the gas of separating from thermal low-pressure separators;
(8) in step (7), the isolated liquid phase of cold low separator is after stripping tower stripping, and at the bottom of stripping tower tower, liquid phase enters separation column, obtains gasoline and diesel oil distillate.
In the inventive method, the heavy benzol that low point of oil of step (4) heat can also a part be circulated to after pre-hydrofining reaction district and filtration mixes, as the charging in pre-hydrofining reaction district, looping back the low point of oil of heat in pre-hydrofining reaction district and the weight ratio of heavy benzol is 1～4:1.
In the inventive method, described heavy benzol is the by product of crude benzole hydrogenation, and its character is as follows: 95～130 ℃ of initial boiling points, do 230～280 ℃, 20 ℃ of density 0.96～0.99g/cm
3, aromaticity content is generally 60wt%～85wt%, and unsaturated compound content is generally 18wt%～25wt%, and sulphur content is 0.9wt%～1.3wt%, and nitrogen content is 0.6wt%～1.3wt%, oxygen level is 1.0wt%～2.0wt%.
In the inventive method, the described low point of oil of the heat that loops back main hydroconversion reaction zone of step (4) is 1～3:1 with the weight ratio of pre-hydrogenation liquid product.
In the inventive method, the operational condition in described pre-hydrofining reaction district is: temperature of reaction is that 100～250 ℃, hydrogen dividing potential drop are that 1.0～6.0MPa, hydrogen to oil volume ratio are that 100:1～600:1, volume space velocity are 1.0～10.0h
-1.
In the inventive method, the operational condition of described main hydroconversion reaction zone is: 230～430 ℃ of temperature of reaction, hydrogen dividing potential drop 4.0～10.0MPa, hydrogen to oil volume ratio 600:1～1800:1, volume space velocity 1.0～2.5h
-1.Preferred operational condition is: 330～360 ℃ of temperature of reaction, hydrogen dividing potential drop 6.0～8.0MPa, hydrogen to oil volume ratio 500:1～1000:1, volume space velocity 2.5～4.0h
-1.
In the inventive method, the operational condition of described hydro-upgrading reaction zone is: 340 ℃～440 ℃ of temperature of reaction, hydrogen dividing potential drop 4.0MPa～12.0MPa, hydrogen to oil volume ratio 500:1～1500:1, volume space velocity 0.5h
-1～4.0h
-1.Preferred operations condition is: 340～380 ℃ of temperature of reaction, hydrogen dividing potential drop 5.0～8.0MPa, hydrogen to oil volume ratio 500:1～900:1, volume space velocity 0.9～1.5h
-1.
In the inventive method, described hydrogenation protecting reaction zone and main hydrofining reaction district can be in same reactors or respectively in different reactors, the volume ratio of described hydrogenation protecting catalyst and Hydrobon catalyst is 1:4～1:8.
In the inventive method, described pre-hydrofining reaction district is used the Hydrobon catalyst with high pore volume and high-specific surface area, catalyzer is take VI B family and/or group VIII metal as active metal component, take aluminum oxide or silicon-containing alumina as carrier, group VIB metal is Mo and/or W, and group VIII metal is Co and/or Ni; The catalyzer preferred property that pre-hydrofining reactor uses is: pore volume 0.35～0.70ml/g, specific surface area is for being preferably 280～400m
2/ g, take oxide compound hydrogenation active metals component concentration as 5%～20%, is preferably 8%～16% in catalyzer.The commodity Hydrobon catalyst that is applicable to above-mentioned character in this area is caught Si catalyst etc. as the FHRS-1 of Fushun Petrochemical Research Institute's development and production.
In the inventive method, the Hydrobon catalyst loading in described main hydroconversion reaction zone is conventional Hydrobon catalyst or pretreating catalyst by hydrocracking, generally take VI B family and/or group VIII metal as active ingredient, take the aluminum oxide of aluminum oxide, silicon-containing alumina or siliceous and phosphorus as carrier, group VIB metal is generally Mo and/or W, and group VIII metal is generally Co and/or Ni.Take the weight of catalyzer as benchmark, group VIB metal content is counted 10wt%～35wt% with oxide compound, and group VIII metal content is counted 3wt%～15wt% with oxide compound, and the character of this catalyzer is as follows: specific surface is 100～350m
2/ g, pore volume is 0.15～0.60ml/g.Main catalyzer have China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute develop 3936,3996, FF-16, FF-26 etc.
In the inventive method, hydrogenation protecting loads hydrogenation protecting catalyst in reaction zone, is mainly used in imurity-removal and part carbon residue, to avoid downstream hydrogenation catalyst coking, the running period of extension fixture.Described hydrogenation protecting catalyst can adopt conventional residual hydrogenation protective material or residuum hydrogenating and metal-eliminating catalyst; generally take VI B family and/or group VIII metal as active ingredient; take aluminum oxide or silicon-containing alumina as carrier; group VIB metal is generally Mo and/or W, and group VIII metal is generally Co and/or Ni.With the weighing scale of catalyzer, active metallic content is counted 0.5wt%～18wt% with oxide compound, preferably composed as follows: group VIB metal content is counted 0.5wt%～15wt% with oxide compound, group VIII metal content is counted 0.5wt%～8wt% with oxide compound, and shape can be hollow cylinder, trifolium shape, Herba Galii Bungei or spherical etc.For example: FZC-103, FZC-200, FZC-100 and the FZC-102B catalyzer of Fushun Petrochemical Research Institute's research and development.
In the inventive method, in described hydro-upgrading reactor, only load catalyst for hydro-upgrading.Catalyst for hydro-upgrading used is the catalyzer with good aromatic saturation and higher selectivity of ring-opening, and generally, take group VIB and/or group VIII metal as active ingredient, group VIB metal is generally Mo and/or W, and group VIII metal is generally Co and/or Ni.The carrier of this catalyzer be in aluminum oxide, silicon-containing alumina and molecular sieve one or more.With the weighing scale of catalyzer, group VIB metal content is counted 10wt%～35wt% with oxide compound, and group VIII metal content is counted 3wt%～15wt% with oxide compound, and molecular sieve content is 5wt%～40wt%, and alumina content is 10wt%～80wt%, and its specific surface is 100m
2/ g～650m
2/ g, pore volume is 0.15mL/g～0.50mL/g.Molecular sieve can be Y zeolite and/or b type molecular sieve etc.As 3963 and FC-18 of China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute's development.
Compared with prior art, the present invention also has the following advantages:
1, because aromaticity content in raw material heavy benzol is higher, as naphthalene, methylnaphthalene etc., the present invention adopts low point of oil circulation go back to main hydroconversion reaction zone of heat, mix the charging as main hydroconversion reaction zone with the pre-hydrofining liquid product of heavy benzol, can effectively reduce like this concentration of these typical compounds in heavy benzol, significantly the temperature rise in hydrofining reaction district, avoid due to temperature rise, cause making the permanent inactivation of catalyzer coking, be conducive to the steady safety operation of device, and can prolong operating period.Meanwhile, solved because temperature rise is too high, and the problem of many reactors or more beds must be set; Also solved because cold hydrogen amount between reactor or bed increases, the problem that causes circulating hydrogen compressor load to increase, this two aspect all can be saved facility investment greatly.
2, because oxygen level in raw material heavy benzol is higher; separation system after hydrofining can be discharged in time to the influential water of catalyst for hydro-upgrading carrier; because water will cause support of the catalyst skeleton to cave in; cause metal accumulation; thereby catalyst activity and stability are had a negative impact; protect so on the one hand the activity of follow-up hydrogenation modifying catalyst; alleviate Liao Zhu hydrofining reaction district processing condition severity simultaneously; contribute to reduce the temperature rise in hydrofining reaction district; can greatly save facility investment, extend the running period of device.Hydrofining liquid product after separation enters hydro-upgrading reactor, make naphthalene compounds not yet completely saturated in hydrotreated product as open loops after hydro-upgrading reaction is first saturated such as naphthanes, generate the alkylbenzene with many side chains, thereby be converted into comparatively ideal diesel component, improve the cetane value of diesel oil distillate, produce qualified diesel oil, and have the advantage that condensation point is low concurrently.
3, in the inventive method, adopt low point of oil circulation Hui Yu hydrofining reaction district of heat, mix the charging as pre-hydrotreating reaction district with raw material heavy benzol, can effectively reduce the concentration of the unsaturated compound such as indenes, coumarone and vinylbenzene in raw material heavy benzol, can significantly reduce the temperature rise in pre-hydrofining reaction district, avoid due to temperature rise, cause making the permanent inactivation of catalyzer coking, be conducive to the steady safety operation of device, and can prolong operating period.Meanwhile, solved because temperature rise is too high, and the problem of many reactors or more beds must be set; Also solved because cold hydrogen amount between reactor or bed increases, the problem that causes circulating hydrogen compressor load to increase, this two aspect all can be saved facility investment greatly.
4, in the inventive method, raw material heavy benzol is first after pre-hydrofining reaction district hydrogenation reaction, entering main hydrofining reaction district further reacts again, can make in heavy benzol the first hydrogenation of unsaturated compound saturated, avoid that Yin Wendu is higher to be generated superpolymer and be accumulated in wherein at interchanger or top, main hydroconversion reaction zone polymerization reaction take place, produce pressure reduction, affect device running period.
5, the present invention is except obtaining clean low-coagulation diesel oil blend component, also by-product part clean gasoline blend component, for the lower heavy benzol of added value provides a kind of working method that improves its economy, not only develop the new purposes of raw material, expand again the raw material sources of clean fuel oil.
Accompanying drawing explanation
Fig. 1 is the block diagram of the inventive method.
Embodiment
1 the invention will be further described by reference to the accompanying drawings.Raw material heavy benzol 1 is after filter 2 filters, enter pre-hydrofining reaction district 4 with new hydrogen 3 and together with recycle hydrogen 7 mixtures of gas-liquid separator 6, contact and carry out pre-hydrofining reaction with Hydrobon catalyst wherein, pre-hydrotreated product 5 is after gas-liquid separator 6 separates, liquid product 8 is with new hydrogen 3 with after mixing from the recycle hydrogen 28 of cold high pressure separator 20, enter main hydroconversion reaction zone 9, contact with Hydrobon catalyst and carry out hydrofining reaction with hydrogenation protecting agent wherein, gained hydrotreated product 10 is after high pressure hot separator 11 separates, liquid product enters thermal low-pressure separators 12, low point of oil 13 of heat is divided into three parts, wherein first part 14 is back to main hydroconversion reaction zone 9, second section 15 enters hydro-upgrading reaction zone 17, contact and react with catalyst for hydro-upgrading, hydro-upgrading product 18 enters cold high pressure separator 20 with high pressure hot separator gas phase 19, Part III 16 is back to pre-hydrofining reaction district 4, mix the charging as pre-hydrofining reaction district 4 with filtered heavy benzol.The gas of cold high pressure separator 20 is through separatory, again after recycle compressor supercharging, a part is mixed into and becomes owner of hydroconversion reaction zone 9 and hydro-upgrading reaction zone 17 with new hydrogen 3 as recycle hydrogen 28, also can be used as cold hydrogen for controlling the beds temperature rise of main hydroconversion reaction zone 9 and hydro-upgrading reaction zone 17.The gas phase 30 that the liquid phase that cold high pressure separator 20 separates separates with thermal low-pressure separators 12 enters cold low separator 21 after mixing, the isolated liquid 22 of cold low separator 21 is after stripping tower 23 air lifts remove hydrogen sulfide and gas products 29, stripping tower bottom liquid phase 24 is removed separation column 25, obtains respectively product gasoline fraction 26 and diesel oil distillate 27 through distillation.
The following examples will be further described present method, but be not limited in this.
Embodiment 1～3
Heavy benzol feedstock property used is in table 1.Embodiment concrete technology flow process is shown in Fig. 1, embodiment 1～3 processing condition and the results are shown in table 2.
In embodiment 1～3; pre-hydrofining reaction district filling Hydrobon catalyst FHRS-1; in embodiment 1 and embodiment 3; main hydroconversion reaction zone is loaded hydrogenation protecting catalyst FZC-103 and Hydrobon catalyst 3936 from top to bottom successively; the admission space of two kinds of catalyzer is than being 1:7; in embodiment 2, main hydroconversion reaction zone is loaded hydrogenation protecting catalyst FZC-103 and Hydrobon catalyst FF-26 from top to bottom successively, and the admission space of two kinds of catalyzer is than being 1:5.In embodiment 1 and embodiment 2,3963 catalyzer are loaded in hydro-upgrading reaction zone, hydro-upgrading reaction zone filling FC-18 catalyzer in embodiment 3.
In embodiment 1～3, hydrofining generates oil after gas-liquid separation, and separating obtained liquid product part loops back main hydrofining reaction district, and part loops back pre-hydrofining reaction district.Wherein, the hydrofining that loops back main hydroconversion reaction zone generates the weight ratio of oil and pre-hydrofining liquid product, and embodiment 1 and embodiment 2 are that 2.0, embodiment 3 is 3.0; Loop back the liquid product in pre-hydrofining reaction district and the weight ratio of heavy benzol, embodiment 1 and embodiment 2 are that 2.5, embodiment 3 is 1.5.
Comparative example 1
In this comparative example, pre-hydrofining reaction district filling Hydrobon catalyst FHRS-1, the admission space of hydrogenation protecting catalyst FZC-103 and 3936, two kinds of catalyzer of Hydrobon catalyst is loaded from top to bottom successively than being 1:5 in main hydroconversion reaction zone.Low point of oil of hydrofining heat neither loops back main hydroconversion reaction zone through separating obtained liquid product, does not also loop back pre-hydrofining reaction district.Concrete technology condition and the results are shown in table 2.
Heavy benzol feedstock property used is in table 1.
Table 1 stock oil character
| Crude title | Heavy benzol |
| Boiling range, ℃ | ? |
| IBP/10% | 102/120 |
| 30%/50% | 137/158 |
| 70%/90% | 188/207 |
| 95%/EBP | 248/275 |
| Density (20 ℃), g/cm 3 | 0.97 |
| S，μg.g -1 | 9930 |
| N，μg.g -1 | 6825 |
| O，μg.g -1 | 14026 |
| Composition, wt% | ? |
| Alkane | 8.2 |
| Naphthenic hydrocarbon | 5.6 |
| Naphthalene | 25.5 |
| Other aromatic hydrocarbons | 41.8 |
| Unsaturated compound | 18.9 |
Table 2 hydrogenation technique condition and diesel oil distillate product property
| Scheme | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
| Pre-hydrofining reaction district | ? | ? | ? | ? |
| Recycle ratio | 2.5:1 | 2.5:1 | 1.5:1 | 0 |
| Catalyzer | FHRS-1 | FHRS-1 | FHRS-1 | FHRS-1 |
| Processing condition | ? | ? | ? | ? |
| Hydrogen dividing potential drop/MPa | 2.0 | 4.0 | 6.0 | 4.0 |
| Temperature of reaction/℃ | 160 | 180 | 200 | 180 |
| Air speed/h -1 | 2.0 | 6.0 | 10.0 | 1.7 |
| Hydrogen to oil volume ratio | 200 | 350 | 500 | 350 |
| 2 hours situations turn round | Normally | Normally | Normally | Temperature runaway |
| Main hydroconversion reaction zone | ? | ? | ? | ? |
| Recycle ratio | 2:1 | 2:1 | 3:1 | 0 |
| Catalyzer | FZC-103/FF-26 | FZC-103/3936 | FZC-103/FF-26 | FZC-103/3936 |
| Processing condition | ? | ? | ? | ? |
| Hydrogen dividing potential drop, MPa | 8.0 | 7.0 | 6.5 | 7.0 |
| Temperature of reaction, ℃ | 360 | 350 | 370 | 350 |
| Air speed, h -1 | 3.5 | 2.5 | 3.0 | 1.0 |
| Hydrogen to oil volume ratio | 800 | 600 | 1000 | 600 |
| Runtime, h | 3000 | 5000 | 7000 | Device is forced to stop work |
| Hydrofining generates oil nature | ? | ? | ? | ? |
| Density (20 ℃), gcm -3 | 0.9105 | 0.9194 | 0.9180 | ? |
| Sulphur content, μ gg -1 | 70 | 76 | 74 | ? |
| Nitrogen content, μ gg -1 | 61 | 69 | 63 | ? |
| Free-water, μ gg -1 | ＜300 | ＜300 | ＜300 | ? |
| Catalyst for hydro-upgrading | 3963 | 3963 | FC-18 | ? |
| Processing condition | ? | ? | ? | ? |
| Hydrogen dividing potential drop, MPa | 6.5 | 8.5 | 7.5 | ? |
| Temperature of reaction, ℃ | 370 | 360 | 350 | ? |
| Volume space velocity when liquid, h -1 | 1.0 | 1.2 | 1.4 | ? |
| Hydrogen to oil volume ratio | 700 | 600 | 800 | ? |
| Diesel product character | ? | ? | ? | ? |
| Yield, wt% | 80.2 | 78.9 | 79.1 | ? |
| Density (20 ℃), gcm -3 | 0.8373 | 0.8322 | 0.8345 | ? |
| Sulphur content/μ gg -1 | 7 | 5 | 6 | ? |
| Condensation point, ℃ | -11 | -16 | -12 | ? |
| Boiling range, ℃ | ? | ? | ? | ? |
| 50% | 182 | 178 | 181 | ? |
| 90% | 242 | 240 | 241 | ? |
| 95% | 263 | 262 | 262 | ? |
| Cetane value | 45.8 | 47.1 | 46.8 | ? |
| Gasoline fraction character | ? | ? | ? | ? |
| Yield, wt% | 19.0 | 19.3 | 20.0 | ? |
| Octane value (RON) | 89.2 | 88.5 | 88.9 | ? |
Can be found out by table 2 data analysis, in comparative example, low point of oil of heat, through neither looping back pre-hydrofining reaction district, does not loop back main hydroconversion reaction zone yet, just occurs temperature runaway phenomenon in device running after 2 hours, and now, device needs shutdown process.In embodiment 1, adopt the mode of low point of oil circulation time main hydroconversion reaction zone of hydrofining heat, in embodiment 2 and embodiment 3, adopt low point of oil of hydrofining heat not only to loop back main hydroconversion reaction zone but also part to loop back the mode in pre-hydrofining reaction district, device smooth running is normal, has improved significantly the running period of device running.
Claims (15)
1. heavy benzene hydrogenation upgrading is produced a clean fuel oil method, and described method comprises:
(1) raw material heavy benzol after filtration, enters pre-hydrofining reaction district with hydrogen after mixing, and contacts carry out hydrofining reaction with Hydrobon catalyst;
(2) the pre-hydrofining products therefrom in step (1) carries out gas-liquid separation through gas-liquid separator, gained liquid product enters main hydroconversion reaction zone, pass through successively hydrogenation protecting reaction zone and main hydrofining reaction district, under hydrogen exists, contact and carry out hydrogenation reaction with Hydrobon catalyst with hydrogenation protecting catalyst successively, obtain hydrotreated product;
(3) hydrotreated product in step (2) carries out gas-liquid separation through high pressure hot separator;
(4) liquid product that in step (3), high pressure hot separator separates enters the further gas-liquid separation of thermal low-pressure separators, and low point of oil part of separating obtained heat loops back main hydroconversion reaction zone;
(5) in step (4), low point of oil of remainder heat enters hydro-upgrading reaction zone, under hydrogen exists, after catalyst for hydro-upgrading contact reacts, obtains hydro-upgrading product;
(6) in step (5) hydro-upgrading product with enter cold high pressure separator from the isolated gas of high pressure hot separator;
(7) liquid that in step (6), cold high pressure separator is separated enters cold low separator with the gas of separating from thermal low-pressure separators;
(8) in step (7), the isolated liquid phase of cold low separator is after stripping tower stripping, and at the bottom of stripping tower tower, liquid phase enters separation column, obtains gasoline and diesel oil distillate.
2. it is characterized in that in accordance with the method for claim 1: in step (4), low point of oil part of separating obtained heat loops back pre-hydrofining reaction district.
3. it is characterized in that in accordance with the method for claim 1: low point of oil of heat that step (4) loops back main hydroconversion reaction zone is 1～3:1 with the weight ratio of pre-hydrogenation liquid product.
4. it is characterized in that in accordance with the method for claim 2: looping back the low point of oil of heat in pre-hydrofining reaction district and the weight ratio of heavy benzol is 1～4:1.
5. in accordance with the method for claim 1; it is characterized in that: described hydrogenation protecting reaction zone and main hydrofining reaction district are in same reactor or respectively in different reactors, and wherein the volume ratio of hydrogenation protecting catalyst and Hydrobon catalyst is 1:4～1:8.
6. in accordance with the method for claim 1, it is characterized in that: described heavy benzol is the by product of crude benzole hydrogenation, and its character is as follows: 95～130 ℃ of initial boiling points, do 230～280 ℃, 20 ℃ of density 0.96～0.99g/cm
3, aromaticity content is 60wt%～85wt%, and unsaturated compound content is 18wt%～25wt%, and sulphur content is 0.9wt%～1.3wt%, and nitrogen content is 0.6wt%～1.3wt%, oxygen level is 1.0wt%～2.0wt%.
7. it is characterized in that in accordance with the method for claim 1: the operational condition in described pre-hydrofining reaction district is: temperature of reaction is that 150～200 ℃, hydrogen dividing potential drop are that 1.0～6.0MPa, hydrogen to oil volume ratio are that 100:1～600:1, volume space velocity are 1.0～10.0h
-1.
8. it is characterized in that in accordance with the method for claim 1: the operational condition of described main hydroconversion reaction zone is: temperature of reaction is that 230～430 ℃, hydrogen dividing potential drop are that 4.0～10.0MPa MPa, hydrogen to oil volume ratio are 600:1～1800:1, volume space velocity 1.0～2.5h
-1.
9. it is characterized in that in accordance with the method for claim 1: the operational condition of described hydro-upgrading reaction zone is: temperature of reaction is that 340～440 ℃, hydrogen dividing potential drop are that 4.0～12.0MPa, hydrogen to oil volume ratio are that 500:1～1500:1, volume space velocity are 0.5～4.0h
-1.
10. in accordance with the method for claim 1, it is characterized in that: described pre-hydrofining reaction district is used the Hydrobon catalyst with high pore volume and high-specific surface area, catalyzer is take VI B family and/or group VIII metal as active metal component, take aluminum oxide or silicon-containing alumina as carrier, group VIB metal is Mo and/or W, and group VIII metal is Co and/or Ni; In catalyzer, in oxide compound, hydrogenation active metals component concentration is 5%～20%, and catalyst property is: pore volume 0.35～0.70mL/g, specific surface area is 280～400m
2/ g.
11. in accordance with the method for claim 1, it is characterized in that: the Hydrobon catalyst that described main hydroconversion reaction zone is used is conventional Hydrobon catalyst or pretreating catalyst by hydrocracking.
12. according to the method described in claim 1 or 11, it is characterized in that: the Hydrobon catalyst that described main hydroconversion reaction zone is used, take VI B family and/or group VIII metal as active ingredient, take the aluminum oxide of aluminum oxide, silicon-containing alumina or siliceous and phosphorus as carrier, group VIB metal is Mo and/or W, group VIII metal is Co and/or Ni, take the weight of catalyzer as benchmark, group VIB metal content is counted 10wt%～35wt% with oxide compound, group VIII metal content is counted 3wt%～15wt% with oxide compound, described catalyst property is that specific surface is 100～350m
2/ g, pore volume is 0.15～0.60mL/g.
13. in accordance with the method for claim 1, it is characterized in that: described hydrogenation protecting catalyst adopts residual hydrogenation protective material or residuum hydrogenating and metal-eliminating catalyst.
14. in accordance with the method for claim 13; it is characterized in that: described hydrogenation protecting catalyst is take VI B family and/or group VIII metal as active ingredient; take aluminum oxide or silicon-containing alumina as carrier; group VIB metal is Mo and/or W; group VIII metal is Co and/or Ni; with the weighing scale of catalyzer, active metallic content is counted 0.5wt%～18wt% with oxide compound.
15. in accordance with the method for claim 1, it is characterized in that: the catalyst for hydro-upgrading that described hydro-upgrading reaction zone adopts is the catalyst for hydro-upgrading with good aromatic saturation and higher selectivity of ring-opening, take group VIB and/or group VIII metal as active ingredient, group VIB metal is Mo and/or W, group VIII metal is Co and/or Ni, the carrier of this catalyzer is aluminum oxide, in silicon-containing alumina and molecular sieve one or more, take the weight of catalyzer as benchmark, group VIB metal content is counted 10wt%～35wt% with oxide compound, group VIII metal content is counted 3wt%～15wt% with oxide compound, molecular sieve content is 5wt%～40wt%, alumina content is 10wt%～80wt%, its character is: specific surface 100m
2/ g ~ 650m
2/ g, pore volume 0.15mL/g ~ 0.50mL/g.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101240193A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Coal tar multistage hydrogenation treatment technique |
| CN101712888A (en) * | 2009-11-26 | 2010-05-26 | 湖南长岭石化科技开发有限公司 | Hydrofining technology of heavy benzol |
| CN102041078A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Method for producing lightweight fuel oil by hydrogenation of deep drawn anthracene oil |
| CN102041075A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Anthracene oil hydrogenation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101240193A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Coal tar multistage hydrogenation treatment technique |
| CN102041078A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Method for producing lightweight fuel oil by hydrogenation of deep drawn anthracene oil |
| CN102041075A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Anthracene oil hydrogenation method |
| CN101712888A (en) * | 2009-11-26 | 2010-05-26 | 湖南长岭石化科技开发有限公司 | Hydrofining technology of heavy benzol |
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