CN103789033B - 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
- Publication number
- CN103789033B CN103789033B CN201210433555.6A CN201210433555A CN103789033B CN 103789033 B CN103789033 B CN 103789033B CN 201210433555 A CN201210433555 A CN 201210433555A CN 103789033 B CN103789033 B CN 103789033B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- upgrading
- hydro
- reaction zone
- hydrogen
- 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.)
- Active
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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 produces the method for clean fuel oil.
Background technology
The scarcity day by day of world petroleum resource, making various non-conventional oil resources processing produce clean fuel oil tech becomes focus, and wherein one of technology is for producing clean fuel oil with Coal Chemical Industry by-product.
Heavy benzol is the by product produced in coal chemical industry crude benzole hydrogenation process for refining process, in crude benzole hydrogenation technological process, raw material crude benzol is separated in multi-stage evaporation device, high boiling component such as trimethylbenzene, naphthalene, indane, coumarone etc. are discharged bottom multi-stage evaporation device as Residual oil, and this part Residual oil is heavy benzol.
Heavy benzol character is generally: initial boiling point 95 ~ 130 DEG C, does 230 ~ 280 DEG C, 20 DEG C 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%, and oxygen level is 1.0wt% ~ 2.0wt%.Although heavy benzol boiling range is comparatively light, 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 being different from petroleum fractions.
Current most domestic producer all using heavy benzol as raw fuel stock or solvent oil process, only has only a few enterprise for the production of coumarone-indene resin, because petroleum resin are more competitive than coumarone indene resin in price and performance etc., 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 difference, also there is irritating smell as solvent oil, directly as not only quality not high and contaminate environment during oil fuel, namely all there is poor product quality, lack competitiveness or the problem of contaminate environment in these purposes at present.
In order to utilize heavy benzol better, 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 improve quality product, improve the added value of raw material to a certain extent, but the hydrofining technology condition that it provides can not make heavy benzol be converted into clean fuel oil production, simultaneously for because of component concentration unsaturated in heavy benzol high, typical compound content is concentrated, the problem that the pre-hydrofining reaction district temperature rise caused is large does not mention solution, because unsaturated compound is as higher in styrene content in heavy benzol, if there is a styrene molecules to carry out pre-hydrofining reaction, so in heavy benzol, other becomes ten thousand more than one hundred million styrene molecules all will react, consequent reaction heat will be very large, if do not take corresponding method, even if liquid hydrogen injection, also may cause reducing temperature rise because applicable circulating hydrogen compressor cannot be chosen, finally cause device temperature runaway, make the permanent inactivation of catalyzer, even burn out reactor, consequence is serious, namely 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 that heavy benzene hydrogenation upgrading produces clean fuel oil.The present invention not only can make heavy benzol produce clean gasoline and diesel product through hydrogenation reaction; and effectively can solve the large problem of hydrofining reaction district temperature rise; the activity stability of protection catalyst for hydro-upgrading, to the operation of the safety and steady of device and prolong operating period favourable.
A kind of heavy benzene hydrogenation upgrading of the present invention produces clean fuel oil method, and described method comprises:
(1) raw material heavy benzol after filtration, enters pre-add hydrogen refining 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, successively through hydrogenation protecting reaction zone and main hydrofining reaction district, in presence of hydrogen, contact with Hydrobon catalyst with hydrogenation protecting catalyst successively and carry out hydrogenation reaction, 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 separating obtained heat low point of oily component loops goes back to main hydroconversion reaction zone;
(5) in step (4), remainder heat low point of oil enters hydro-upgrading reaction zone, in presence of hydrogen, 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 separated 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, step (4) heat low point of oil can also a part be circulated to pre-hydrofining reaction district and filtration after heavy benzol mix, as the charging in pre-hydrofining reaction district, loop back the heat low point of oil 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: initial boiling point 95 ~ 130 DEG C, does 230 ~ 280 DEG C, 20 DEG C 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%, and oxygen level is 1.0wt% ~ 2.0wt%.
In the inventive method, the weight ratio of the low point of oil of the heat looping back main hydroconversion reaction zone described in step (4) and pre-hydrogenation liquid product is 1 ~ 3:1.
In the inventive method, the operational condition in described pre-hydrofining reaction district is: temperature of reaction is 100 ~ 250 DEG C, hydrogen dividing potential drop is 1.0 ~ 6.0MPa, hydrogen to oil volume ratio is 100:1 ~ 600:1, volume space velocity is 1.0 ~ 10.0h
-1.
In the inventive method, the operational condition of described main hydroconversion reaction zone is: temperature of reaction 230 ~ 430 DEG C, 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: temperature of reaction 330 ~ 360 DEG C, 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: temperature of reaction 340 DEG C ~ 440 DEG C, 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: temperature of reaction 340 ~ 380 DEG C, 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 in same reactors or respectively in different reactors, and 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 uses the Hydrobon catalyst with high pore volume and high-specific surface area, catalyzer is for active metal component with VI B race and/or group VIII metal, with aluminum oxide or silicon-containing alumina for 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, and specific surface area is for being preferably 280 ~ 400m
2/ g, in catalyzer with oxide basis hydrogenation active metals component concentration for 5% ~ 20%, be preferably 8% ~ 16%.The FHRS-1 of commodity Hydrobon catalyst as Fushun Petrochemical Research Institute's development and production being applicable to above-mentioned character in this area catches Si catalyst etc.
In the inventive method, the Hydrobon catalyst loaded in described main hydroconversion reaction zone is conventional Hydrobon catalyst or pretreating catalyst by hydrocracking, generally with VI B race and/or group VIII metal for active ingredient, with the aluminum oxide of aluminum oxide, silicon-containing alumina or siliceous and phosphorus for carrier, group VIB metal is generally Mo and/or W, and group VIII metal is generally Co and/or Ni.With the weight of catalyzer for benchmark, group VIB metal content take oxide basis as 10wt% ~ 35wt%, and group VIII metal content take oxide basis as 3wt% ~ 15wt%, 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 to 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 the coking of downstream hydrogenation catalyzer, the running period of extension fixture.Described hydrogenation protecting catalyst can adopt the agent of conventional residual oil hydrogenation protecting or residuum hydrogenating and metal-eliminating catalyst; generally with VI B race and/or group VIII metal for active ingredient; with aluminum oxide or silicon-containing alumina for 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 take oxide basis as 0.5wt% ~ 18wt%, preferably composed as follows: group VIB metal content take oxide basis as 0.5wt% ~ 15wt%, group VIII metal content take oxide basis as 0.5wt% ~ 8wt%, and shape can be hollow cylinder, trilobes, Herba Galii Bungei or spherical etc.Such as: FZC-103, FZC-200, FZC-100 and 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, generally with group VIB and/or group VIII metal for 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 take oxide basis as 10wt% ~ 35wt%, and group VIII metal content take oxide basis as 3wt% ~ 15wt%, 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 that China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute develops.
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 heat low point of oil circulation go back to main hydroconversion reaction zone, mix the charging as main hydroconversion reaction zone with heavy benzol pre-hydrogenation refined liquid phase product, effectively can reduce the concentration of these typical compounds in heavy benzol like this, can the temperature rise in significantly 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, solve because temperature rise is too high, and the problem of multiple stage reactor or more beds must be set; Also solve because hydrogen amount cold between reactor or bed increases, cause the problem that circulating hydrogen compressor load increases, facility investment all can be saved greatly in this two aspect.
2, because oxygen level in raw material heavy benzol is higher; separation system after hydrofining can be discharged the influential water of catalyst for hydro-upgrading carrier in time; because water will cause support of the catalyst structure collapse; cause metal accumulation; thus catalyst activity and stability are had a negative impact; such one side protects the activity of follow-up hydrogenation modifying catalyst; alleviate main hydrofining reaction district processing condition severity simultaneously; contribute to the temperature rise reducing hydrofining reaction district; greatly can 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, thus be converted into comparatively ideal diesel component, improve the cetane value of diesel oil distillate, produce qualified diesel oil, and have the low advantage of condensation point concurrently.
3, in the inventive method, adopt heat low point of oil circulation Hui Yu hydrofining reaction district, the charging as pre-hydrotreating reaction district is mixed with raw material heavy benzol, effectively can reduce the concentration of the unsaturated compound such as indenes, coumarone and vinylbenzene in raw material heavy benzol, significantly can 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, solve because temperature rise is too high, and the problem of multiple stage reactor or more beds must be set; Also solve because hydrogen amount cold between reactor or bed increases, cause the problem that circulating hydrogen compressor load increases, facility investment all can be saved greatly in this two aspect.
4, in the inventive method, raw material heavy benzol is first after pre-hydrofining reaction district hydrogenation reaction, enter main hydrofining reaction district again to react further, the first hydrotreated lube base oil of unsaturated compound in heavy benzol can be made, avoid that Yin Wendu is higher to be generated superpolymer at interchanger or top, main hydroconversion reaction zone polymerization reaction take place and be accumulated in wherein, produce pressure reduction, affect device running period.
5, the present invention is except obtaining the low-coagulation diesel oil blend component that cleans, also by-product part clean gasoline blend component, for the heavy benzol that added value is lower provides a kind of working method improving its economy, not only develop the novelty teabag of raw material, expanded 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, with new hydrogen 3 and from gas-liquid separator 6 recycle hydrogen 7 mixture together with enter pre-hydrofining reaction district 4, contact with Hydrobon catalyst wherein and carry out pre-hydrofining reaction, pre-hydrotreated product 5 is after gas-liquid separator 6 is separated, 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, to contact with Hydrobon catalyst with hydrogenation protecting agent wherein and carry out hydrofining reaction, gained hydrotreated product 10 is after high pressure hot separator 11 is separated, liquid product enters thermal low-pressure separators 12, heat low point of oil 13 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 with catalyst for hydro-upgrading and react, hydro-upgrading product 18 and high pressure hot separator gas phase 19 enter cold high pressure separator 20, Part III 16 is back to pre-hydrofining reaction district 4, the charging as pre-hydrofining reaction district 4 is mixed 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 as recycle hydrogen 28 and new hydrogen 3 becomes owner of hydroconversion reaction zone 9 and hydro-upgrading reaction zone 17, also can 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 is separated is separated with thermal low-pressure separators 12 enters cold low separator 21 after mixing, the isolated liquid 22 of cold low separator 21 removes after hydrogen sulfide and gas products 29 through stripping tower 23 air lift, stripping tower bottom liquid phase 24 removes separation column 25, obtains product gasoline fraction 26 and diesel oil distillate 27 respectively 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; hydrogenation protecting catalyst FZC-103 and Hydrobon catalyst 3936 are loaded from top to bottom successively in main hydroconversion reaction zone; the admission space of two kinds of catalyzer is than being 1:7; in embodiment 2, hydrogenation protecting catalyst FZC-103 and Hydrobon catalyst FF-26 is loaded from top to bottom successively in main hydroconversion reaction zone, 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, separating obtained liquid product component loops Hui Zhu hydrofining reaction district, component loops Hui Yu hydrofining reaction district.Wherein, the hydrofining looping back main hydroconversion reaction zone generates weight ratio that is oily and pre-hydrogenation refined liquid phase product, and embodiment 1 and embodiment 2 are 2.0, and embodiment 3 is 3.0; Loop back the pre-liquid product in hydrofining reaction district and the weight ratio of heavy benzol, embodiment 1 and embodiment 2 are 2.5, and 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 Hydrobon catalyst 3936, two kinds of catalyzer is loaded from top to bottom successively than being 1:5 in main hydroconversion reaction zone.Hydrofining heat low point of oil 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, DEG C | |
| IBP/10% | 102/120 |
| 30%/50% | 137/158 |
| 70%/90% | 188/207 |
| 95%/EBP | 248/275 |
| Density (20 DEG C), 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 process conditions 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/DEG C | 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 |
| Operate 2 hours situations | 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, DEG C | 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 DEG C), 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, DEG C | 370 | 360 | 350 | |
| Volume space velocity during 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 DEG C), gcm -3 | 0.8373 | 0.8322 | 0.8345 | |
| Sulphur content/μ gg -1 | 7 | 5 | 6 | |
| Condensation point, DEG C | -11 | -16 | -12 | |
| Boiling range, DEG C | ||||
| 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 |
As can be seen from table 2 data analysis, in comparative example, heat low point of oil is through neither looping back pre-hydrofining reaction district, and also do not loop back main hydroconversion reaction zone, after device operates 2 hours, just occur temperature runaway phenomenon, now, device needs shutdown process.In embodiment 1, adopt the mode of hydrofining heat low point of oil circulation time main hydroconversion reaction zone, in embodiment 2 and embodiment 3, hydrofining heat low point of oil is adopted not only to loop back main hydroconversion reaction zone but also the mode in component loops Hui Yu hydrofining reaction district, device smooth running is normal, considerably improves the running period of device running.
Claims (13)
1. heavy benzene hydrogenation upgrading produces a clean fuel oil method, and described method comprises:
(1) raw material heavy benzol after filtration, enters pre-add hydrogen refining 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, successively through hydrogenation protecting reaction zone and main hydrofining reaction district, in presence of hydrogen, contact with Hydrobon catalyst with hydrogenation protecting catalyst successively and carry out hydrogenation reaction, 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 separating obtained heat low point of oily component loops goes back to main hydroconversion reaction zone;
(5) in step (4), remainder heat low point of oil enters hydro-upgrading reaction zone, in presence of hydrogen, 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 separated 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;
Wherein, the oily component loops Hui Yu hydrofining reaction district of low point of separating obtained heat in step (4), the operational condition of described hydro-upgrading reaction zone is: temperature of reaction is 340 ~ 380 DEG C, hydrogen dividing potential drop is 6.0 ~ 8.0MPa, hydrogen to oil volume ratio is 500:1 ~ 1000:1, volume space velocity is 0.9 ~ 1.5h
-1.
2. in accordance with the method for claim 1, it is characterized in that: step (4) loops back heat low point of oil of main hydroconversion reaction zone and the weight ratio of pre-hydrogenation liquid product is 1 ~ 3:1.
3. in accordance with the method for claim 1, it is characterized in that: loop back the heat low point of oil in pre-hydrofining reaction district and the weight ratio of heavy benzol is 1 ~ 4:1.
4. 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.
5. 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: initial boiling point 95 ~ 130 DEG C, do 230 ~ 280 DEG C, 20 DEG C 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%, and oxygen level is 1.0wt% ~ 2.0wt%.
6. in accordance with the method for claim 1, it is characterized in that: the operational condition in described pre-hydrofining reaction district is: temperature of reaction is 150 ~ 200 DEG C, hydrogen dividing potential drop is 1.0 ~ 6.0MPa, hydrogen to oil volume ratio is 100:1 ~ 600:1, volume space velocity is 1.0 ~ 10.0h
-1.
7. in accordance with the method for claim 1, it is characterized in that: the operational condition of described main hydroconversion reaction zone is: temperature of reaction is 230 ~ 430 DEG C, hydrogen dividing potential drop is 4.0 ~ 10.0MPa MPa, hydrogen to oil volume ratio is 600:1 ~ 1800:1, volume space velocity 1.0 ~ 2.5h
-1.
8. in accordance with the method for claim 1, it is characterized in that: described pre-hydrofining reaction district uses the Hydrobon catalyst with high pore volume and high-specific surface area, catalyzer with VI B race and/or group VIII metal for active metal component, with aluminum oxide or silicon-containing alumina for carrier, group VIB metal is Mo and/or W, and group VIII metal is Co and/or Ni; With oxide basis in catalyzer, hydrogenation active metals component concentration is 5% ~ 20%, and catalyst property is: pore volume 0.35 ~ 0.70mL/g, and specific surface area is 280 ~ 400m
2/ g.
9. in accordance with the method for claim 1, it is characterized in that: the Hydrobon catalyst that described main hydroconversion reaction zone uses, is Hydrobon catalyst or the pretreating catalyst by hydrocracking of routine.
10. according to the method described in claim 1 or 9, it is characterized in that: the Hydrobon catalyst that described main hydroconversion reaction zone uses, with VI B race and/or group VIII metal for active ingredient, with the aluminum oxide of aluminum oxide, silicon-containing alumina or siliceous and phosphorus for carrier, group VIB metal is Mo and/or W, group VIII metal is Co and/or Ni, with the weight of catalyzer for benchmark, group VIB metal content take oxide basis as 10wt% ~ 35wt%, group VIII metal content take oxide basis as 3wt% ~ 15wt%, described catalyst property is, specific surface is 100 ~ 350m
2/ g, pore volume is 0.15 ~ 0.60mL/g.
11. 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.
12. in accordance with the method for claim 11; it is characterized in that: described hydrogenation protecting catalyst with VI B race and/or group VIII metal for active ingredient; with aluminum oxide or silicon-containing alumina for 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 take oxide basis as 0.5wt% ~ 18wt%.
13. 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, with group VIB and/or group VIII metal for 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, in the weight of catalyzer for benchmark, group VIB metal content take oxide basis as 10wt% ~ 35wt%, group VIII metal content take oxide basis as 3wt% ~ 15wt%, 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210433555.6A CN103789033B (en) | 2012-11-05 | 2012-11-05 | Method for hydro-upgrading of heavy benzene to produce clean fuel oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210433555.6A CN103789033B (en) | 2012-11-05 | 2012-11-05 | Method for hydro-upgrading of heavy benzene to produce clean fuel oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103789033A CN103789033A (en) | 2014-05-14 |
| CN103789033B true CN103789033B (en) | 2015-07-22 |
Family
ID=50665097
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210433555.6A Active CN103789033B (en) | 2012-11-05 | 2012-11-05 | Method for hydro-upgrading of heavy benzene to produce clean fuel oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103789033B (en) |
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 |
-
2012
- 2012-11-05 CN CN201210433555.6A patent/CN103789033B/en active Active
Patent 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103789033A (en) | 2014-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100590182C (en) | Method for producing cleaning oil from coal-tar oil | |
| CN100558863C (en) | A kind of combined method of producing cleaning oil from coal-tar oil | |
| CN101294107B (en) | Method for preparing fuel oil with coal oil hydrogenation | |
| CN103305269B (en) | Method for producing gasoline and diesel by directly hydrogenating medium and low temperature coal tar | |
| CN102041075B (en) | Anthracene oil hydrogenation method | |
| CN102851074A (en) | Combination processing method of coal tar | |
| CN102041073B (en) | Hydrocracking method for anthracene oil | |
| CN104004541B (en) | A kind of preparation method of coal-based high arene underwater content stock oil | |
| CN102041047B (en) | Heavy oil hydrogenation modifying method | |
| CN103789035B (en) | A kind of heavy benzene hydrogenation produces clean fuel oil method | |
| CN101619240B (en) | Method for producing aromatic hydrocarbon solvent oil by using pyrolysis gasoline | |
| CN106147852B (en) | A kind of method by producing diesel by utilizing coal tar component | |
| CN1175090C (en) | Method for producing the clean diean diesel oil with low sulfur and low arene | |
| CN104774648B (en) | A kind of heavy benzene hydrogenation refines the method for clean fuel oil | |
| CN103789025B (en) | Heavy benzene hydro-upgrading method | |
| CN106947528A (en) | A kind of hydrogenating conversion process containing aromatics diesel | |
| CN103789031B (en) | A kind of heavy benzene hydrogenation process for purification | |
| CN102911721B (en) | Method for removing olefins from reformate through liquid phase circulation selective hydrogenation | |
| CN103695032A (en) | Modification method of heavy diesel oil | |
| CN103789033B (en) | Method for hydro-upgrading of heavy benzene to produce clean fuel oil | |
| CN105623731A (en) | Method for preparing high-density coal-based jet fuel by adopting anthracene oil as raw material | |
| CN109988610A (en) | A kind of flexible two-segment hydrocracking method | |
| CN102041076B (en) | Method for producing light fuel oil by hydrogenating anthracene oil | |
| CN102041080A (en) | Integrated method for hydrocracking and producing ethylene cracking material | |
| CN101089143A (en) | Inferior fraction oil upgrading process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |