CN103374400A - Combination method for producing high-quality kerosene through hydrogenation - Google Patents
Combination method for producing high-quality kerosene through hydrogenation Download PDFInfo
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- CN103374400A CN103374400A CN2012101306867A CN201210130686A CN103374400A CN 103374400 A CN103374400 A CN 103374400A CN 2012101306867 A CN2012101306867 A CN 2012101306867A CN 201210130686 A CN201210130686 A CN 201210130686A CN 103374400 A CN103374400 A CN 103374400A
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Abstract
The invention relates to a combination method for producing high-quality kerosene through hydrogenation. The combination method comprises the steps that firstly, under the condition of hydrogenation, biolipid and recycle hydrogen are mixed and pass through a hydrotreating reaction zone, the gas obtained by separating a hydrotreating generated material flow is recycled, the liquid obtained by separation, raw kerosene and the recycle hydrogen are mixed and pass through a hydrofining reaction zone and then enter a hydro-upgrading reaction zone at least comprising hydrogenation catalysts with isomerization performance, and the liquid obtained by separating a hydro-upgrading generated material flow is continuously fractionated, thus obtaining naphtha and kerosene products, wherein in the reaction state, the hydrogenation active components of the hydrogenation catalysts used in the hydrotreating reaction zone are Pt and/or Pd in the reduction state. Compared with the prior art, the method has the advantages that not only can the storage stability of the biolipid as fuel oil be effectively improved but also the high-quality kerosene can be directly produced.
Description
Technical field
The invention belongs to the working method of renewable energy source, relate to a kind of method of hydrotreating, particularly a kind of take bio-oil and boat coal cut as stock oil, the combined hydrogenation method of direct production high-quality burning oil.
Background technology
The energy in the global range is mainly derived from fossil energy at present, mainly comprise coal and oil, and motor for automobile fuel is mainly derived from oil.Fossil energy belongs to Nonrenewable energy resources, and resource is day by day exhausted, and oil more has the trend of heaviness and the aggravation of in poor quality degree.Sustained economic development, environmental regulation increasingly stringent along with the world, emission standard is more and more higher, various countries are very vigorous to the demand of light clean fuel, when all requiring oil company and R﹠D institution that existing oil Refining Technologies is improved, these constantly seek new oil substitutes, and produce satisfactory product with minimum cost, especially can be to the development and utilization of renewable resource.
Bio oil, fat are renewable resourcess, and therefore its comprehensive utilization also obtains worldwide extensive attention, is devoted to take its research as the raw material production cleaning product with all strength.The first-generation biofuel that produces thing diesel oil (being generally fatty acid methyl ester) by the method for utilizing transesterify next life has been proven technique.But because oxygen level is high in this class biofuel, although many countries and regions have been put into effect the standard of biofuel successively, can not be applicable to all oil engines.If bio oil, fat are produced automotive fuel by the method for deep hydrogenation, be about to that oxygen is all removed or major part is removed and produced the product that meets the automotive fuel standard, this method can directly satisfy the requirement of existing market.
Existing bio oil, the fat hydrogenation method is produced the processing technology of automotive fuel, US20060186020, EP1693432, CN101321847A, CN200710012090.6, CN200680045053.9, CN200710065393.4, CN200780035038.0, CN200710012208.5, CN200780028314.0 and CN101029245A etc. disclose the vegetables oil hydroconversion process, adopt the coker gasoline cut, diesel oil distillate (straight-run diesel oil, LCO and coker gas oil), petroleum hydrocarbon cut and the bio oil such as wax oil cut or residue oil fraction, fat directly is mixed into hydroconversion reaction zone, under the effect of hydrogen, by beds, produce the raw material of diesel product or preparing ethylene by steam cracking etc.US5705722 discloses vegetables oil such as containing unsaturated fatty acids, fat and animal oil mixing back end hydrogenation is produced the diesel oil blending component of diesel oil distillate scope.
EP1741767 and EP1741768 disclose a kind of method of producing diesel oil distillate with animal-plant oil, be mainly animal-plant oil and at first pass through hydrotreatment, then by the isomerization catalyst bed layer, obtain the low freezing point diesel fuel component, but owing to generate water in the hydrotreatment process, isomerization catalyst is caused very adverse influence, and device can not long-period stable operation.
Comprise in the bio-oil hydrogenation process of aforesaid method that one of subject matter that runs into is that the bed carbon distribution causes that the pressure drop rising makes shorten the more catalyst changeout of need to often stopping work running period.Particularly separately take bio oil, fat as raw material or bio-oil blending ratio when higher, more be subject to obvious impact the running period of hydrogenation catalyst.Carry out conventional raw material according to this area general knowledge and add hydrogen pretreatment (such as the saturated or shallow degree hydrofining of hydrogenation of routine etc.), although prolong to some extent (generally can reach 500 hours) running period, but still can not solve long period steady running problem.Contain multiple different organo-functional group in the bio-oil, the reaction of these organo-functional groups in hydrogenation process is comparatively complicated, influence each other between the different reactions, the major cause that affects bio-oil raw material hydrogenation process stability is still indefinite, and therefore improving run stability is the major issue that this area need to solve.And when producing light ends also because of the catalyst activity shortcomings such as the running period that causes is short that are affected.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method of hydrotreating of producing high-quality burning oil, take bio-oil and kerosene(oil)fraction as stock oil, direct production high-quality burning oil product under the condition of hydrogenation, the characteristics such as it is stable to have a hydrogenation process, and running period is long.
The combined method that a kind of hydrogenation method of the present invention is produced high-quality burning oil is characterized in that comprising following content:
(a) one or more in the bio-oil are the first stock oil, and one or more of virgin kerosene or secondary processing kerosene(oil)fraction are the second stock oil;
(b) under the hydrotreatment operational condition, the first stock oil is by the first paragraph reaction zone of at least two hydrogenators, load hydrogenation catalyst in the hydrogenator, bio-oil and hydrogen is the hydrogenator by cold operation at first, then by the hydrogenator of high-temperature operation, under response behaviour, the active ingredient of hydrogenation catalyst is Pt and/or the Pd of sulphided state, the first reaction zone hydrogenation effluent is separated into gas phase and liquid phase, and gas-phase dehydration recycles after processing;
(c) under the hydrofining operational condition, step (b) separate obtain liquid and the second stock oil under hydroconversion condition by loading the second reaction zone of Hydrobon catalyst, then under hydroconversion condition, continue to enter the 3rd reaction zone that comprises at least catalyst for hydro-upgrading;
(d) gas phase of the 3rd reaction zone reaction effluent recycles, and the liquid phase of the 3rd reaction zone reaction effluent is carried out fractionation by distillation and obtained petroleum naphtha and high-quality burning oil cut.
In the inventive method step (a), the bio oil, the fat that use can comprise vegetables oil or animal grease, vegetables oil comprises one or more in soybean oil, peanut oil, Viscotrol C, rapeseed oil, Semen Maydis oil, sweet oil, plam oil, Oleum Cocois, tung oil, oleum lini, sesame oil, Oleum Gossypii semen, curcas oil, sunflower seed oil and the rice bran wet goods, and animal grease comprises butter, lard, sheep oil, fish oil and roasts in the grease that other animals obtain etc. one or more.Being preferably carbon chain lengths is C
12～C
16Bio-oil, such as cocounut oil etc.
In the inventive method step (a), virgin kerosene is generally the kerosene(oil)fraction that normal vacuum fractionation obtains, the virgin kerosene of preferred intermediate base crude oil and naphthenic base crude.Secondary processing kerosene is generally the secondary petroleum refining process, the kerosene(oil)fraction that obtains such as technological processs such as hydrocracking, catalytic cracking, hydrotreatment, coking, thermally splitting, viscosity breaking, ethene, and the kerosene(oil)fraction of coal tar.
In the inventive method step (a), the volume ratio of the first stock oil and the second stock oil is 1:99 ~ 99:1, preferred 5:95 ~ 95:5, preferably 10:90 ~ 90:10.
In the inventive method step (b), be prohibited from entering the material of sulfur-bearing, nitrogenous impurity in the first reaction zone.
In the inventive method step (b), the hydroprocessing condition of the hydrogenator of cold operation is generally reaction pressure 3.0MPa ~ 20.0MPa, is preferably 4.0MPa ~ 18.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.5h
-1~ 6.0h
-1, 120 ℃ ~ 280 ℃ of average reaction temperature; The operational condition of the hydrogenator of high-temperature operation is reaction pressure 3.0MPa ~ 20.0MPa, is preferably 4.0MPa ~ 18.0MPa, hydrogen to oil volume ratio 200:1 ~ 3000:1, volume space velocity 0.5h
-1~ 6.0h
-1, average reaction temperature than the hydrogenator of cold operation high 50 ℃ ~ 300 ℃, preferred high 80 ℃ ~ 220 ℃.Between the hydrogenator of cold operation and the hydrogenator of high-temperature operation process furnace or interchanger are set, with the temperature of reaction of the hydrogenator of adjusting high-temperature operation.
At first by in the hydrogenator of cold operation, the active ingredient of the hydrogenation catalyst of use is in the element quality of precious metals pt and/or Pd for bio-oil, and the content of noble metal hydrogenation active ingredient is 0.01%～0.50%.Reaction mass continues the hydrogenator by high-temperature operation, and the active ingredient of the hydrogenation catalyst that uses in the hydrogenator of high-temperature operation is in the element of precious metals pt and/or Pd, and the content of noble metal hydrogenation active ingredient is 0.10%～3.50%.The active component content of catalyzer is higher than the catalyzer in the cold operation hydrogenator in the hydrogenator of preferred high-temperature operation, preferred high 0.1 ~ 3 percentage point (in the element quality).Reactor generally can arrange 2 ~ 5, is preferably 2.A kind of catalyzer can be loaded in each hydrogenator, also multiple catalysts can be loaded.The carrier of hydrogenation catalyst is generally aluminum oxide, amorphous silicon aluminium, silicon oxide, titanium oxide etc., can contain other auxiliary agent simultaneously, such as P, Si, B, Ti, Zr etc.Can adopt the commercial catalyst, also can be by the existing method preparation in this area.Noble metal catalyst such as Fushun Petrochemical Research Institute (FRIPP) develop the HDO-18 catalyzer, also can be by described method preparations such as CN00123141.3.The catalyzer of the first reaction zone carries out conventional reduction before use to be processed, and the catalyzer of other reaction zone carries out conventional sulfidizing before use.The reduction treatment condition are generally 200～400 ℃ of pressure 2～15MPa and temperature, with hydrogen to catalyst reduction 1～15 hour.
In the inventive method step (c), the hydroprocessing condition of second reaction zone is generally reaction pressure 1.0MPa ~ 20.0MPa, can be identical with the first reaction zone, can be not identical yet, and hydrogen to oil volume ratio is 150:1 ~ 2500:1, volume space velocity is 0.3h
-1~ 10.0h
-1, 130 ℃ ~ 420 ℃ of average reaction temperature; Preferred operational condition is hydrogen to oil volume ratio 200:1 ~ 2000:1, volume space velocity 0.4h
-1~ 8.0h
-1, 150 ℃ ~ 400 ℃ of average reaction temperature.
In the inventive method step (c), second should distinguish the catalyzer that uses is the Hydrobon catalyst of routine, commercial hydrogenation catalyst mainly contains, the hydrogenation catalysts such as 481-3, the FDS-4A that develops such as Fushun Petrochemical Research Institute (FRIPP), FH-40A, FH-40B, FH-40C, the hydrogenation catalysts such as the TK-527 of Topsor company, TK-561, TK-568, the KF-840 of AKZO company, KF-842, the HR-416 of Inst Francais Du Petrole, HR-448, the HR-416 of Inst Francais Du Petrole, HR-448.
In the inventive method step (c), the hydroprocessing condition of the 3rd reaction zone is generally reaction pressure 1.0MPa ~ 20.0MPa, and than the low 0MPa ~ 2.0MPa of second reaction zone reaction pressure, hydrogen to oil volume ratio is 200:1 ~ 2500:1, and volume space velocity is 0.3h
-1~ 10.0h
-1, 130 ℃ ~ 420 ℃ of average reaction temperature; Preferred operational condition is hydrogen to oil volume ratio 300:1 ~ 2000:1, volume space velocity 0.4h
-1~ 8.0h
-1, 150 ℃ ~ 400 ℃ of average reaction temperature.
In the inventive method step (c), the catalyst for hydro-upgrading of the 3rd reaction zone has isomery function and cracking function, can contain the components such as beta-molecular sieve, SAPO-11 molecular sieve, SAPO-41, NU-10 molecular sieve or ZSM-22 molecular sieve, the weight content of described molecular sieve in catalyzer is generally 3%～30%, is preferably 5%～20%.The hydrogenation active metals component of catalyst for hydro-upgrading (one or more among W, Mo, Ni and the Co) is generally 10%～40% in the weight content of oxide compound.The commercial catalysts that the second segment reaction zone uses mainly contains, FC-14, the FC-16 that develops such as Fushun Petrochemical Research Institute (FRIPP), FC-20 etc.
In the inventive method, three reaction zones can use independent recycle hydrogen system, also can the common recycle hydrogen system, and also can any two reaction zone common recycle hydrogen systems.Preferred the first reaction zone uses independent recycle hydrogen system.
In the inventive method, can be at an amount of Hydrobon catalyst that replenishes of arranging at last of the 3rd reaction zone catalyst for hydro-upgrading bed, with material hydrogenation such as issuable a small amount of alkene in the hydro-upgrading process.
In the inventive method, the 3rd reaction zone uses suitable catalyzer and operational condition, can obtain high-quality kerosene product.Can adjust the yield of kerosene(oil)fraction by adjusting the conditions such as temperature of reaction of the 3rd reaction zone, in general, temperature of reaction raises, and the cracking performance of modifying catalyst improves, and the amount that bio-oil is cracked into kerosene increases.Also can adjust as required the internal circulating load of tail oil, further adjust the productive rate of kerosene.The tail oil circulation can be circulated to arbitrary reaction zone, preferred cycle to the three reaction zones.
The bio-oil hydrogenation is produced the method for automotive fuel in the prior art, generally need to the petroleum fractions hybrid process of larger proportion, otherwise can not guarantee running period, perhaps directly by hydrofining-catalyst for hydro-upgrading bed, the component poor stability of cracking catalyst activity can not long-term operation.The present invention is by optimizing grating technology and the operational condition of using catalyzer, the first reaction zone hydrofining (hydrogenation catalyst of grating and suitable processing condition), the second reaction zone diesel oil hydrofining, the 3rd reaction zone hydro-upgrading pour point depression, can be directly take bio-oil and kerosene as raw material production high-quality burning oil product, solved the problem that the bio-oil hydrogenation unit can not the long period steady running.And the conventional hydrogen pretreatment that adds does not still reach required stability, the conventional hydrogen pretreatment that adds generally can be realized running period about 500 hours, the use properties of catalyzer obviously descends, and obvious rising falls in the reacting system pressure when using fixed bed, needs more catalyst changeout.And the present invention program, after 1000 hours, the Pressure Drop of catalyst performance and reactive system does not all have considerable change in steady running, and according to this trend, estimating fully can steady running 1～3 year.
Description of drawings
Fig. 1 is the combined method principle flow chart that hydrogenation method of the present invention is produced high-quality burning oil.
Embodiment
Method of the present invention is specific as follows: the mixing oil of one or more in the bio-oil is as stock oil, under the hydroprocessing condition, stock oil and hydrogen are by comprising the first reaction zone of at least two kinds of hydrogenation catalysts, the hydrotreatment that obtains generates logistics and separates the gas circulation use that obtains in high-pressure separator, also can go out system, the liquid distillate that obtains; The liquid distillate of the first reaction zone, diesel raw material and hydrogen are mixed into and comprise hydrorefined second reaction zone, the hydrofining that obtains generates logistics and continues by comprising the 3rd reaction zone with isomery performance catalyst for hydro-upgrading, the hydro-upgrading that obtains generates logistics and separate the gas circulation use that obtains in high-pressure separator, also can go out system, the liquid fractionation obtains following products: one or more in gas, petroleum naphtha, the kerosene.The bio-oil that embodiment uses is the commercially available prod, filtering solid impurity before using.
Further specify particular case of the present invention below by embodiment.
The chief component of table 1 hydrogenation catalyst and character.
| Catalyzer | Catalyzer 1 | Catalyzer 2 | Catalyzer 3 | Catalyst for refining | Modifying catalyst |
| Catalyzer forms | ? | ? | ? | ? | ? |
| Pt，wt% | 0.4 | 0.05 | 1.2 | ? | ? |
| Pd，wt% | 0.1 | 0.1 | ? | ? | ? |
| MoO 3，wt% | ? | ? | ? | 15.0 | 20.5 |
| NiO，wt% | ? | ? | ? | 3.5 | 3.9 |
| Beta-molecular sieve, wt% | ? | ? | ? | ? | 8.0 |
| Alumina supporter, wt% | Surplus | Surplus | Surplus | Surplus | Surplus |
| The main character of catalyzer | ? | ? | ? | ? | ? |
| Specific surface, m 2/g | >160 | >160 | >160 | >160 | >160 |
| Pore volume, ml/g | >0.30 | >0.30 | 0.33 | 0.36 | >0.34 |
The main character of table 2 diesel raw material oil.
| Catalyzer | Virgin kerosene | Mix kerosene |
| Density, g/cm 3 | 0.799 | 0.842 |
| The cut scope, ℃ | 130~230 | 150~270 |
| Sulphur content, μ g/g | 1100 | 900 |
| Nitrogen content, μ g/g | 15 | 120 |
| Smoke point, mm | 24 | 18 |
Table 3 embodiment processing condition and test-results.
| The first reaction zone processing condition | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Stock oil | Oleum Gossypii semen | Soybean oil | Rapeseed oil | Plam oil |
| The cold operation reactor | ? | ? | ? | ? |
| Catalyzer | Catalyzer 2 | Catalyzer 2/ catalyzer 1 | Catalyzer 1 | Catalyzer 2/ catalyzer 1 |
| The catalyst volume ratio | 100 | 30:70 | 100 | 20:80 |
| Reaction pressure, MPa | 10.0 | 8.0 | 15.0 | 6.0 |
| The entrance hydrogen to oil volume ratio | 1500:1 | 800:1 | 600:1 | 1000:1 |
| Volume space velocity, h -1 | 3.5 | 2.0 | 0.5 | 1.0 |
| Average reaction temperature, ℃ | 220 | 255 | 180 | 200 |
| The high-temperature operation reactor | ? | ? | ? | ? |
| Catalyzer | Catalyzer 3 | Catalyzer 3 | Catalyzer 3 | Catalyzer 3 |
| Reaction pressure, MPa | 10.0 | 8.0 | 15.0 | 6.0 |
| The entrance hydrogen to oil volume ratio | 1500:1 | 800:1 | 600:1 | 1000:1 |
| Volume space velocity, h -1 | 2.0 | 1.5 | 4.0 | 1.5 |
| Average reaction temperature, ℃ | 350 | 350 | 380 | 345 |
| Stock oil | The first reaction zone liquid and virgin kerosene volume ratio 60:40 | The first reaction zone liquid and virgin kerosene volume ratio 50:50 | The first reaction zone liquid and virgin kerosene volume ratio 60:40 | The first reaction zone liquid and virgin kerosene volume ratio 30:70 |
| The second reaction zone processing condition | ? | ? | ? | ? |
| Catalyzer | Catalyst for refining | Catalyst for refining | Catalyst for refining | Catalyst for refining |
| Stock oil | Virgin kerosene | Virgin kerosene | Mix kerosene | Mix kerosene |
| Reaction pressure, MPa | 3.0 | 12.0 | 8.0 | 6.0 |
| The entrance hydrogen to oil volume ratio | 200:1 | 500:1 | 800:1 | 500:1 |
| Volume space velocity, h -1 | 1.0 | 2.0 | 3.5 | 6.0 |
| Average reaction temperature, ℃ | 270 | 310 | 32 | 340 |
| The 3rd reaction zone processing condition | ? | ? | ? | ? |
| Catalyzer | Modifying catalyst | Modifying catalyst | Modifying catalyst | Modifying catalyst |
| Reaction pressure, MPa | 3.0 | 12.0 | 8.0 | 6.0 |
| The entrance hydrogen to oil volume ratio | 300:1 | 1000:1 | 1000:1 | 600:1 |
| Volume space velocity, h -1 | 2.0 | 1.0 | 1.5 | 4.0 |
| Average reaction temperature, ℃ | 280 | 300 | 290 | 320 |
| The kerosene product | ? | ? | ? | ? |
| Density, g/cm 3 | 0.791 | 0.793 | 0.822 | 0.813 |
| Sulphur content, μ g/g | <0.5 | <0.5 | <0.5 | <0.5 |
| Smoke point, mm | 30 | 29 | 25 | 26 |
Table 4 embodiment processing condition and test-results.
| The first reaction zone processing condition | Embodiment 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Stock oil | Soybean oil | Soybean oil/mixing kerosene | Soybean oil/mixing kerosene | Soybean oil/mixing kerosene |
| The stock oil ratio | 100 | 50:50 | 50:50 | 50:50 |
| The cold operation reactor | ? | ? | ? | ? |
| Catalyzer | Catalyzer 2 | Catalyzer 3/ catalyst for refining/modifying catalyst | Catalyzer 3/ catalyst for refining/modifying catalyst | Catalyzer 3/ catalyst for refining/modifying catalyst |
| The catalyst volume ratio | 100 | 33:33:33 | 33:33:33 | 33:33:33 |
| Reaction pressure, MPa | 8.0 | 8.0 | 8.0 | 8.0 |
| The entrance hydrogen to oil volume ratio | 1000:1 | 1000:1 | 1000:1 | 1000:1 |
| Volume space velocity, h -1 | 2.0 | 0.68 | 0.68 | 0.68 |
| Average reaction temperature, ℃ | 220 | 350 | 370 | 380 |
| The high-temperature operation reactor | ? | ? | ? | ? |
| Catalyzer | Catalyzer 3 | ? | ? | ? |
| Reaction pressure, MPa | 8.0 | ? | ? | ? |
| The entrance hydrogen to oil volume ratio | 1000:1 | ? | ? | ? |
| Volume space velocity, h -1 | 2.0 | ? | ? | ? |
| Average reaction temperature, ℃ | 350 | ? | ? | ? |
| Stock oil | The first reaction zone liquid with mix kerosene volume ratio 50:50 | ? | ? | ? |
| The second reaction zone processing condition | ? | ? | ? | ? |
| Catalyzer | Catalyst for refining | ? | ? | ? |
| Stock oil | Virgin kerosene | ? | ? | ? |
| Reaction pressure, MPa | 8.0 | ? | ? | ? |
| The entrance hydrogen to oil volume ratio | 500:1 | ? | ? | ? |
| Volume space velocity, h -1 | 2.0 | ? | ? | ? |
| Average reaction temperature, ℃ | 260 | ? | ? | ? |
| The 3rd reaction zone processing condition | ? | ? | ? | ? |
| Catalyzer | Modifying catalyst | ? | ? | ? |
| Reaction pressure, MPa | 8.0 | ? | ? | ? |
| The entrance hydrogen to oil volume ratio | 1000:1 | ? | ? | ? |
| Volume space velocity, h -1 | 2.0 | ? | ? | ? |
| Average reaction temperature, ℃ | 350 | ? | ? | ? |
| Runtime, h | 1000 | 100 | 300 | 600 |
| Total pressure drop, MPa | 0.04 | 0.04 | 0.16 | 0.30 |
| The kerosene product | ? | ? | ? | ? |
| Density, g/cm 3 | 0.795 | 0.795 | 0.816 | 0.835 |
| Sulphur content, μ g/g | <0.5 | <0.5 | 50 | 630 |
| Smoke point, mm | 29 | 29 | 26 | 23 |
Can be found out by embodiment, bio-oil and kerosene feedstock oil can be produced the high-quality burning oil product by the method for hydrotreating of present technique, perhaps high-quality burning oil blend component, and can realize long-period stable operation, turn round after 1000 hours, the reactive system pressure drop is not risen substantially, and carbon deposition quantity only has about 3.2wt% on the catalyzer, belong to the balance carbon deposition quantity, do not affect the catalyzer use properties.
Claims (12)
1. a hydrogenation method is produced the combined method that adds of high-quality burning oil, it is characterized in that comprising following content:
(a) one or more in the bio-oil are the first stock oil, and one or more of virgin kerosene or secondary processing kerosene(oil)fraction are the second stock oil;
(b) under the hydrotreatment operational condition, the first stock oil is by the first paragraph reaction zone of at least two hydrogenators, load hydrogenation catalyst in the hydrogenator, bio-oil and hydrogen is the hydrogenator by cold operation at first, then by the hydrogenator of high-temperature operation, under response behaviour, the active ingredient of hydrogenation catalyst is Pt and/or the Pd of reduction-state, the first reaction zone hydrogenation effluent is separated into gas phase and liquid phase, and gas-phase dehydration recycles after processing;
(c) under the hydrofining operational condition, step (b) separate obtain liquid and the second stock oil under hydroconversion condition by loading the second reaction zone of Hydrobon catalyst, then under hydroconversion condition, continue to enter the 3rd reaction zone that comprises at least catalyst for hydro-upgrading;
(d) gas phase of the 3rd reaction zone reaction effluent recycles, and the liquid phase of the 3rd reaction zone reaction effluent is carried out fractionation by distillation and obtained petroleum naphtha and high-quality burning oil cut.
2. in accordance with the method for claim 1, it is characterized in that: in the step (a), the bio-oil of use comprises vegetables oil or animal grease.
3. in accordance with the method for claim 1, it is characterized in that: in the step (a), the virgin kerosene that uses comprises the kerosene(oil)fraction that atmospheric and vacuum distillation of petroleum obtains, the secondary processing kerosene(oil)fraction comprises that hydrocracking, catalytic cracking, catalytically cracked material add the kerosene(oil)fraction that hydrogen pretreatment, coking, viscosity breaking or thermal cracker are produced, or the kerosene(oil)fraction of coal tar.
4. in accordance with the method for claim 1, it is characterized in that: in the step (b), be prohibited from entering the material of sulfur-bearing, nitrogenous impurity in the first reaction zone.
5. in accordance with the method for claim 1, it is characterized in that: in the step (b), the reaction pressure 3.0MPa of the hydrogenator of cold operation ~ 20.0MPa, hydrogen to oil volume ratio are 200:1 ~ 3000:1, and volume space velocity is 0.5h
-1~ 6.0h
-1, 120 ℃ ~ 280 ℃ of average reaction temperature; The operational condition of the hydrogenator of high-temperature operation is reaction pressure 3.0MPa ~ 20.0MPa, hydrogen to oil volume ratio 200:1 ~ 3000:1, volume space velocity 0.5h
-1~ 6.0h
-1, average reaction temperature than the hydrogenator of cold operation high 50 ℃ ~ 300 ℃.
6. in accordance with the method for claim 1, it is characterized in that: in rapid (b), the average reaction temperature of the hydrogenator of high-temperature operation is higher 80 ~ 220 ℃ than the hydrogenator of cold operation step by step.
7. according to claim 1 and 4 described methods, it is characterized in that: in the step (b), in the hydrogenator of the cold operation that reaction mass at first passes through, the active ingredient of the hydrogenation catalyst that uses is in the element quality of precious metals pt and/or Pd, and the content of noble metal hydrogenation active ingredient is 0.01%～0.50%; Reaction mass continues the hydrogenator by high-temperature operation, and the active ingredient of the hydrogenation catalyst that uses in the hydrogenator of high-temperature operation is in the element of precious metals pt and/or Pd, and the content of noble metal hydrogenation active ingredient is 0.10%～3.50%.
8. in accordance with the method for claim 6, it is characterized in that: the active component content of catalyzer is higher than 0.1 ~ 3 percentage point of catalyzer in the cold operation hydrogenator in the element quality in the hydrogenator of high-temperature operation.
9. in accordance with the method for claim 1, it is characterized in that: in the step (c), the reaction pressure of second reaction zone is 1.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 150:1 ~ 2500:1, and volume space velocity is 0.3h
-1~ 10.0h
-1, average reaction temperature is 130 ℃ ~ 420 ℃; Preferred hydrogen to oil volume ratio is 200:1 ~ 2000:1, and volume space velocity is 0.4h
-1~ 8.0h
-1, average reaction temperature is 150 ℃ ~ 400 ℃.
10. in accordance with the method for claim 1, it is characterized in that: in the step (c), the reaction pressure of the 3rd reaction zone is 1.0MPa ~ 20.0MPa, than the low 0MPa ~ 2.0MPa of reaction pressure of second reaction zone, hydrogen to oil volume ratio is 200:1 ~ 2500:1, and volume space velocity is 0.3h
-1~ 10.0h
-1, average reaction temperature is 130 ℃ ~ 420 ℃; Preferred hydrogen to oil volume ratio is 300:1 ~ 2000:1, and volume space velocity is 0.4h
-1~ 8.0h
-1, average reaction temperature is 150 ℃ ~ 400 ℃.
11. in accordance with the method for claim 1, it is characterized in that: in the step (c), contain beta-molecular sieve, SAPO-11 molecular sieve, SAPO-41, NU-10 molecular sieve or ZSM-22 molecular sieve in the catalyst for hydro-upgrading of the 3rd reaction zone, the hydrogenation active metals component of catalyst for hydro-upgrading is take the weight content of oxide compound as 10%～40%.
12. in accordance with the method for claim 1, it is characterized in that: it is characterized in that in the step (a), the volume ratio of the first stock oil and the second stock oil is 10:90 ~ 90:10.
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|---|---|---|---|
| CN201210130686.7A CN103374400B (en) | 2012-04-29 | 2012-04-29 | Hydrogenation method produces the combined method of high-quality burning oil |
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|---|---|---|---|
| CN201210130686.7A CN103374400B (en) | 2012-04-29 | 2012-04-29 | Hydrogenation method produces the combined method of high-quality burning oil |
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|---|---|
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| CN103374400B CN103374400B (en) | 2016-01-06 |
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Citations (4)
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| CN101321847A (en) * | 2005-11-30 | 2008-12-10 | 新日本石油株式会社 | Hydrorefining process and hydrorefined oil |
| EP1693432B1 (en) * | 2005-02-18 | 2009-09-30 | Petroleo Brasileiro S.A. - Petrobras | Vegetable oil hydroconversion process |
| CN101617029A (en) * | 2007-02-20 | 2009-12-30 | 国际壳牌研究有限公司 | Produce the method for paraffinic hydrocarbons |
| WO2011112660A2 (en) * | 2010-03-09 | 2011-09-15 | Exxonmobil Research And Engineering Company | Dewaxing of renewable diesel fuel |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1693432B1 (en) * | 2005-02-18 | 2009-09-30 | Petroleo Brasileiro S.A. - Petrobras | Vegetable oil hydroconversion process |
| CN101321847A (en) * | 2005-11-30 | 2008-12-10 | 新日本石油株式会社 | Hydrorefining process and hydrorefined oil |
| CN101617029A (en) * | 2007-02-20 | 2009-12-30 | 国际壳牌研究有限公司 | Produce the method for paraffinic hydrocarbons |
| WO2011112660A2 (en) * | 2010-03-09 | 2011-09-15 | Exxonmobil Research And Engineering Company | Dewaxing of renewable diesel fuel |
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