CN101760234B - Hydrogenation method for improving cetane number of secondary processing diesel oil - Google Patents
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Abstract
The invention relates to a hydrogenation method for improving the cetane number of secondary processing diesel oil, which comprises the following steps: mixing secondary processing diesel oil and vegetable oil and/or animal fat; carrying out hydrogenation reaction by mixed ingredients and hydrogenation refining catalysts through contact in the existence of hydrogen; and cooling, separating and fractionating reaction outflow materials to obtain diesel oil products with mixed ingredients as the reference. The method provided by the invention can process low-quality diesel oil distillate with high sulfur content, high nitrogen content and small cetane number. The clean diesel oil products with low sulfur content, high polycyclic aromatic hydrocarbon and large cetane number can be obtained. Because the addition proportion of the vegetable oil is controlled, the influence on the hydrogenation catalysts by water generated in the reaction is reduced, the device operation period is prolonged, and in addition, the yield of obtained diesel oil products is high.
Description
Technical field
The invention belongs to a kind of in the situation that there is the method for refining hydrocarbon ils under hydrogen, more particularly, is a kind of method of hydrotreating that improves cetane number of secondary processing diesel oil.
Background technology
Along with improving constantly of environmental protection requirement, people are also more and more higher to the vehicle fuel specification requirement.Worldwide, in up-to-date fuel specification, the diesel oil index has been made to strict control.Mainly that sulphur content to diesel product has had stricter restriction.For example, the Europe III emission standard of Europe enforcement from 2000, the sulphur content of regulation derv fuel oil is less than 350 μ g/g, and in the Europe IV emission standard come into effect in 2005, sulphur content requires to be reduced to below 50 μ g/g, expectation is in the Europe V standard of implementing in 2009, and sulphur content further is reduced to below 10 μ g/g.Simultaneously, various new diesel oil standards have also been made strict regulation to product density, polycyclic aromatic hydrocarbon content and cetane value.To this, China has started to implement gradually European fuel standard.In 2005 and 2008, come into effect respectively III, Europe, Europe IV emission standard in cities such as Beijing, Shanghai, planned to carry out in 2010 years the diesel oil index of Euro V emissions.As can be seen here, how producing clean diesel is the significant problem that each enterprise of great oil refining faces.
At present, China does not carry out strict division to city motor diesel oil and fuel diesel, and the secondary processing diesel oil in finished diesel fuel is as quite large as the ratio of the poor ignition quality fuels such as catalytic cracking diesel oil, coker gas oil.In general, catalytic cracking diesel oil is second-rate.With new diesel oil regulation, compare, not only the foreign matter content such as sulphur, nitrogen is high for catalytic cracking diesel oil, and the content of alkene and aromatic hydrocarbons is high, and cetane value is very low.Its cetane value is generally 20～30, compares with the diesel product specification that there is a big difference.Therefore, how to improve the quality of this part diesel oil, become and produce a clean diesel difficult problem.
As everyone knows, can effectively improve the diesel product quality by hydrotreatment.The sulphur content of diesel product can be reduced to below 350 μ g/g by hydrorefined method, even can meet the requirement of the Europe IV emission standard that is less than 50 μ g/g.But hydrorefined method is very little to producing effects of the character such as cetane value of improving catalytic cracking diesel oil.Generally be merely able to make diesel-fuel cetane number to improve 3～5 units.Therefore, each oil company and research institution have all developed hydro-upgrading or hydrocracking process and the applicable catalyzer thereof of processing poor quality catalytic cracking diesel both at home and abroad.Can obtain by the open loop cracking reaction diesel product that cetane value is higher.But, owing to all containing the molecular sieve of some amount in hydro-upgrading or hydrocracking catalyst, can reduce the yield of diesel product in hydrogenation process, reduced the diesel product amount.Simultaneously, the operational volume air speed of general hydro-upgrading and hydrocracking all is less than hydrofining, and running cost and plant investment are larger.
A kind of method of improving the catalytic cracking diesel oil cetane value is disclosed in CN1289832A.The method is used two kinds of catalyzer: a kind of non-noble metal hydrogenation catalyst for refining and a kind of catalyst for hydro-upgrading that contains molecular sieve.In the hydrogen dividing potential drop, be 4.5～8.0MPa, 320～440 ℃ of temperature of reaction, volume space velocity 0.4～2h
-1, hydrogen to oil volume ratio 500～800Nm
3/ m
3condition under, can make the diesel product cetane value improve 10 units, the heavy % in diesel yield>90.
On the other hand, vegetables oil more and more is subject to common people's attention as a kind of renewable resources.The plant oil composition is mainly lipid acid or the fatty acid ester of long-chain, after deoxygenation and chain rupture, can obtain the diesel oil distillate that cetane value is very high.Therefore, up-to-date research can be raw material production high hexadecane value component with vegetables oil.But due to sulfur-bearing hardly in vegetables oil, in order to make hydrogenation catalyst, can keep sulphided state, need regularly to reactive system, to supplement sulfide.Make process cost increase.Simultaneously, owing to generating a large amount of water after the vegetables oil hydrogenation, for conventional hydrogenation catalyst, water-content is too high can affect intensity and the activity stability of catalyzer, thereby affects the device operational cycle.
US 5705722 has introduced a kind of method that moving (planting) thing oil hydrogenation is produced the high hexadecane value blend component.Animal oil (or vegetables oil) under hydroconversion condition and under the existence of hydrogen with Co-Mo or Ni-Mo catalyzer contact reacts, obtain a kind of liquid of diesel oil distillate scope, through separating, fractionation obtains the additive of high hexadecane value.Hydrogenation conditions wherein is: hydrogen dividing potential drop 4～15MPa, 370～450 ℃ of temperature of reaction, volume space velocity 0.5～5h
-1.
In US 2006/0186020A1, introduced a kind of to mix catalytic cracking diesel oil, coker gas oil and the mixing raw material thereof of 1～75 heavy % vegetables oil.Use a kind of non-noble metal hydrogenation catalyst for refining, the catalyst activity metal component is NiMo or CoMo.In the hydrogen dividing potential drop, be 4.0～10.0MPa, 320～400 ℃ of average reaction temperature, volume space velocity 0.5～2h
-1, hydrogen to oil volume ratio 200～1000Nm
3/ m
3condition under, can obtain the diesel product that cetane value is high, density is low, oxidation stability is good, it is large that cetane value improves the amplitude improved than the diesel oil distillate individual curing.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of method of hydrotreating of secondary processing diesel oil inferior as raw material production high hexadecane value diesel component of take.
Method provided by the invention comprises: secondary processing diesel oil mixes with vegetables oil and/or animal grease, its mixing raw material is under the existence of hydrogen, with Hydrobon catalyst, contact, at 300～450 ℃ of average reaction temperature, hydrogen dividing potential drop 3.2～8.0MPa, volume space velocity 2.1～6.0h
-1, hydrogen to oil volume ratio 300～800Nm
3/ m
3condition under carry out hydrogenation reaction, its reaction effluent obtains diesel product after cooling, separation and fractionation, take mixing raw material as benchmark, by weight, described vegetables oil and/or the animal grease ratio in mixing raw material is 5～35%.
Adopt method provided by the invention, can process high-sulfur, high nitrogen, low-cetane poor-quality diesel-oil by cut fraction.Can be under the operational condition comparatively relaxed, obtain that sulphur content is low, polycyclic aromatic hydrocarbon content and the high clean diesel product of cetane value.Quality product is improved largely than raw material, is good diesel oil blending component.The present invention adopts conventional hydrofining flow process, flow process is simple, working pressure is low, facility investment and process cost all lower.Simultaneously, controlled the mixed ratio of vegetables oil, reduced the impact of water generation reaction on activity of hydrocatalyst, extended the device operational cycle, and the diesel product yield obtained is high.
Embodiment
In the diesel product index, cetane value principal reaction diesel product combustionproperty.The diesel combustion that cetane value is high is even, and thermo-efficiency is high; And the heat that the combustion processes of the low diesel oil of cetane value is sent is inhomogeneous, has increased fuel consumption.Therefore, the new diesel product specification of quality has all proposed higher requirement to diesel-fuel cetane number.IIIHe Europe, Europe VI emission standard requires respectively the cetane value of diesel product to reach more than 46 and 51.
The height of diesel cetane-number is determined by its chemical constitution and fractions consisting.The cetane value Changing Pattern of each family's hydro carbons is: the different hydrocarbons of same carbon number is with the cetane value of alkane for the highest, and alkene, isomeric alkane and naphthenic hydrocarbon are placed in the middle, and the aromatic hydrocarbon especially cetane value of condensed-nuclei aromatics is minimum.The hydro carbons of same structure is along with the increase cetane value of carbon number increases.
The secondary processing means, as catalytic cracking is that the level of crude oil processing improves in refinery, realize the heavy oil lighting, one of important means of voluminous gasoline, diesel oil.Because the feedstock property of processing is poor, and the reaction occurred is cracking reaction, the unsaturated hydrocarbons of catalytic cracking diesel oil and aromaticity content are all higher, thereby the cetane value of catalytic cracking diesel oil is very low, usually be less than 25, differ greatly with current diesel product index request.
On the other hand, contain C in vegetables oil
12～C
20triglyceride level or tri-fatty class material.It can obtain C after hydrogenation deoxidation and chain rupture
12～C
20paraffinic hydrocarbons, this cut has very high cetane value.
By above analysis and understanding to diesel oil distillate hydrocarbon composition and cetane value and composition, the specific embodiment of the present invention is:
The secondary processing diesel oil inferior of take mixes a certain amount of vegetables oil and/or animal grease is raw material, under the existence of hydrogen, with Hydrobon catalyst, contacts, and obtains the diesel product that cetane value improves.
Described hydrofining reaction condition is: 300～450 ℃ of average reaction temperature, preferably 330～380 ℃; Hydrogen dividing potential drop 3.2～8.0MPa, preferably 4.0～6.4MPa; Volume space velocity 2.1～6h
-1, preferred 2.1～4.0h
-1; Hydrogen to oil volume ratio 300～800Nm
3/ m
3, preferred 400～600Nm
3/ m
3.
Hydrogenation products enters successively high-pressure separator and light pressure separator carries out gas-liquid separation, and separating obtained hydrogen-rich gas Returning reactor entrance after circulating hydrogen compressor boosts mixes with in stock oil; The liquid phase stream of gained enters fractionating system, obtains naphtha fraction, fine-quality diesel oil product after fractionation.
Because the reaction of vegetables oil hydrogenation deoxidation can produce water, reduce hydrogenation catalyst intensity for fear of these moisture, cause the hydrogenation catalyst mechanical damage, increase beds pressure reduction, so need to control the ratio that vegetables oil mixes.Take mixing raw material as benchmark, and by weight, described vegetables oil and/or the animal grease ratio in mixing raw material is 5～35%, is preferably 5～30%.The boiling spread of described mixing raw material is 180～700 ℃.
Described secondary processing diesel oil is selected from one or more in catalytic cracking diesel oil, coker gas oil, catalytic pyrolysis diesel oil, visbreaking diesel oil, thermo-cracking diesel oil, direct liquefying diesel oil of coal.
Described vegetables oil is one or more that are selected from plam oil, soybean oil, rapeseed oil, Oleum Gossypii semen, Semen Maydis oil, Rice pollard oil, sunflower oil, peanut oil, Viscotrol C, sesame oil, Fructus Zanthoxyli oil, tea oil, Oleum Cocois, sweet oil, coptis wood oil, tung oil, rosin oil, Chinese vegetable tallow, and described animal grease is selected from one or more in lard, butter, sheep oil, fish oil.
Described Hydrobon catalyst is non-noble metal supported catalyzer, carrier is unformed aluminum oxide and/or silica-alumina supports, the metal component loaded on this carrier is at least one in base metal in VIB or VIII family, the group vib metal is preferably Mo and/or W, and VIII family metal is preferably Co and/or Ni.
Preferred described Hydrobon catalyst, take catalyzer as benchmark, it consists of: the heavy % of nickel oxide 1～10, molybdenum oxide and Tungsten oxide 99.999 sum are 10～50 heavy %, the heavy % of fluorine 1～10, the heavy % of phosphorus oxide 0.5～8, surplus is silica-alumina, take described carrier as benchmark, and the content of the silicon oxide in preferred silica-alumina is 2～45 heavy %, and the content of aluminum oxide is 55～98 heavy %; Further the content of preferential oxidation silicon is 5～40 heavy %, and the content of aluminum oxide is 60～95 heavy %.Described silica-alumina has specific surface and the pore volume of conventional silica-alumina carrier, and the specific surface of preferential oxidation silicon-aluminum oxide is 150～350m
2/ g, more preferably 180～300m
2/ g, the pore volume of preferential oxidation silicon-aluminum oxide is 0.4～1ml/g, more preferably 0.5～0.8ml/g.
Described Hydrobon catalyst contains and is selected from containing one or more in oxygen or nitrogenous organism, and preferred oxygen-containing organic compound is selected from one or more in Organic Alcohol, organic acid; Preferred organic compounds containing nitrogen is selected from one or more in organic amine, organic ammonium salt.For example, oxygenatedchemicals can be ethylene glycol, glycerol, polyoxyethylene glycol (molecular weight is 200-1500), Diethylene Glycol, butyleneglycol, acetic acid, toxilic acid, oxalic acid, nitrilotriacetic acid, 1, one or more in 2-CDTA, citric acid, tartrate, oxysuccinic acid, organic compounds containing nitrogen can be quadrol, EDTA and ammonium salt thereof.Described organism is 0.03-2 with take the mol ratio of nickel, molybdenum and tungsten sum of oxide compound, is preferably 0.08-1.5.The preferred Hydrobon catalyst of the present invention, reactive behavior is high, can be under the reaction conditions comparatively relaxed, the sulphur in the effective elimination raw material, nitrogen impurity, and, because its Hydrogenation is good, also be conducive to the carrying out of aromatic saturation reaction.
In preferred situation, the upstream of described Hydrobon catalyst also is filled with the hydrogenation protecting agent, take integer catalyzer as benchmark, and by volume, the filling ratio of described hydrogenation protecting agent is 1～30%.
This hydrogenation protecting agent can load on the catalyzer on unformed aluminum oxide and/or silica-alumina supports at least one base metal in VIB and VIII family.This hydrogenation protecting catalyst has larger pore volume and specific surface area usually, and for example pore volume is generally 0.5-1.0ml/g, and specific surface area is generally 120-220m
2/ g.In the agent of the top of Hydrobon catalyst filling hydrogenation protecting, reduce the impact of the water of vegetables oil hydrogenation deoxidation reaction gained on Hydrobon catalyst, thus the activity cycle and the stability that extend Hydrobon catalyst.
In preferred situation, the downstream of described Hydrobon catalyst also is filled with catalyst for hydro-upgrading, take integer catalyzer as benchmark, and by volume, the filling ratio of described hydrogenation protecting agent is 1～30%.
Described catalyst for hydro-upgrading contains a kind of carrier and loads on molybdenum and/or tungsten and nickel and/or the cobalt on this carrier, in oxide compound and take the catalyzer total amount as benchmark, the content of molybdenum and/or tungsten is 10～35 heavy %, the heavy % of content 1～15 of nickel and/or cobalt, this carrier is comprised of aluminum oxide and zeolite, and the weight ratio of aluminum oxide and zeolite is 90: 10～50: 50.Described aluminum oxide is the aluminum oxide be composited according to the weight ratio of 75: 25～50: 50 by little porous aluminum oxide and macroporous aluminium oxide, wherein, little porous aluminum oxide is that the pore volume that diameter is less than 80 dust holes accounts for the aluminum oxide of total pore volume more than 95%, and the pore volume that macroporous aluminium oxide is diameter 60-600 dust hole accounts for the aluminum oxide of total pore volume more than 70%.Described zeolite is selected from one or more in faujusite, mordenite, zeolite L, omega zeolite, ZSM-4 zeolite, Beta zeolite, preferred y-type zeolite, and particularly preferred zeolite is that total acid content is 0.02 to being less than 0.5 mmole/gram.
The present invention's catalyst for hydro-upgrading used has the good shape open loop ability of selecting, and can make the open loop cracking of the above cyclic aromatic compounds of dicyclo in raw material, thereby reach the reduction polycyclic aromatic hydrocarbon content, improves cetane value and falls low-density purpose.Simultaneously, due to hydrocracking, the isomery of polycyclic aromatic hydrocarbons, reduced the space steric effect of difficult desulfurization species, for the further ultra-deep hydrodesulfuration in back provides condition.Research shows, the chemical reaction of double ring arene is followed following approach: after most of double ring arene hydrogenation is saturated, become naphthane, become two Yuans naphthenic hydrocarbon after the further hydrogenation of part naphthane is saturated, another part naphthane becomes mononuclear aromatics through the open loop cracking reaction, and the mononuclear aromatics of the part further saturated single-ring naphthene that becomes of hydrogenation again.Above-mentioned reaction process, except the open loop cracking reaction of naphthane does not have reversed reaction, all the other hydrogenation saturated reactions all have reversed reaction to occur, and therefore a corresponding chemical equilibrium is arranged.The catalyst for hydro-upgrading that the present invention uses has good open loop cracking ability, promoted the generation that naphthane open loop cracking is the mononuclear aromatics reaction, thereby broken the chemical equilibrium of whole reaction network, make whole reaction to carry out smoothly along the saturated course of repeated hydrogenation after naphthane open loop cracking, thereby reach the purpose that improves the product cetane value.
The following examples will be further described method provided by the invention, but not thereby limiting the invention.
Hydrobon catalyst (trade names are RS-1000), hydrogenation protecting agent (RG-1), catalyst for hydro-upgrading (trade names are RIC-1) used in embodiment.Above-mentioned catalyzer is China Petrochemical Corp.'s catalyzer Chang Ling branch office and produces.
In embodiment, stock oil A used is that a kind of diesel oil from the heavy catalytic cracking is mixed 5 heavy % plam oils.Stock oil B is that a kind of diesel oil from the heavy catalytic cracking is mixed 10 heavy % plam oils.Stock oil C is that diesel oil from the heavy catalytic cracking is mixed 30 heavy % plam oils.Stock oil D is that diesel oil from the heavy catalytic cracking is mixed 50 heavy % plam oils.The main character of various raw materials is as shown in table 1.
Embodiment 1
Stock oil A contacts and is reacted with Hydrobon catalyst under hydrorefined condition, its resultant of reaction is after refrigerated separation, the hydrogen-rich gas of gained is recycle hydrogen, and the liquid fraction of gained enters fractionating system, and obtaining is naphtha fraction and fine-quality diesel oil cut on a small quantity.Be filled with the hydrogenation protecting agent in the upstream of Hydrobon catalyst, the hydrogenation protecting agent is 1: 9 with the admission space ratio of Hydrobon catalyst.The reaction conditions of the present embodiment is as shown in table 2, and by above-mentioned flow process continuous operation, after 1000 hours, the diesel product main character is as shown in table 3.As can be seen from Table 3, the sulphur content of diesel product is 50 μ g/g, and cetane value is 38.4, than raw material, has improved more than 13.9 units and diesel product yield can reach 98 heavy %.
Embodiment 2
Stock oil B and hydrogen are successively through two reaction zones, with Hydrobon catalyst, with catalyst for hydro-upgrading, contact successively, carry out respectively hydrofining and selective opening cracking reaction, the admission space ratio of Hydrobon catalyst and catalyst for hydro-upgrading is 8: 2, after resultant of reaction is cooling, the hydrogen-rich gas of gained is recycle hydrogen, and the liquid fraction of gained enters fractionating system, is cut into naphtha fraction and fine-quality diesel oil cut.The reaction conditions of the present embodiment is as shown in table 2, and by above-mentioned flow process continuous operation, after 1000 hours, the diesel product main character is as shown in table 3.As can be seen from Table 3, the sulphur content of diesel product is 22 μ g/g, reaches Europe IV emission standard.The diesel product cetane value reaches 42.6, with raw material, compares, and has improved 15.7 units, is the clean diesel blend component of high-quality; And diesel product yield reaches 95 heavily more than %.
Embodiment 3
Stock oil C is reacted under the effect of Hydrobon catalyst, and its resultant of reaction is after refrigerated separation, and the hydrogen-rich gas of gained is recycle hydrogen, and the liquid fraction of gained enters fractionating system, and obtaining is naphtha fraction and fine-quality diesel oil cut on a small quantity.The reaction conditions of the present embodiment is as shown in table 2, and by above-mentioned flow process continuous operation, after 1000 hours, the diesel product main character is as shown in table 3.As can be seen from Table 3, the sulphur content of diesel product, for being less than 50 μ g/g, reaches the requirement of Europe IV emission standard to sulphur content; The diesel product cetane value has improved 10.9 units than raw material, and diesel yield is more than 98 heavy %.
Comparative Examples 1
Stock oil D is reacted under the effect of Hydrobon catalyst, and its resultant of reaction is after refrigerated separation, and the hydrogen-rich gas of gained is recycle hydrogen, and the liquid fraction of gained enters fractionating system, and obtaining is naphtha fraction and fine-quality diesel oil cut on a small quantity.Its reaction conditions is identical with embodiment 3, and by above-mentioned flow process continuous operation, after 800 hours, the present embodiment test-results is in Table 4.Result by table 4 can be found out: when palmitic mixed ratio increases to 50 heavy %, the character of hydrogenated products is improved to impact little.But diesel product yield is by decrease; Because water generation reaction increases considerably, can have a strong impact on the activity stability of hydrogenation catalyst simultaneously.
Table 1 stock oil character
| Raw material | Stock oil A | Stock oil B | Stock oil C | Stock oil D |
| Density (20 ℃), g/cm 3 | 0.9192 | 0.9189 | 0.9180 | 0.9170 |
| Sulphur content, % by weight | 0.40 | 0.38 | 0.30 | 0.22 |
| Nitrogen content, μ g/g | 442 | 419 | 330 | 236 |
| Oxygen level, % by weight | 0.86 | 1.35 | 3.58 | 5.80 |
| Boiling range (D86), ℃ | ||||
| Initial boiling point | 206 | 213 | 225 | 233 |
| 50％ | 289 | 300 | 319 | 369 |
| Final boiling point (95%) | 408 | 637 | 641 | 655 |
| Cetane value | 24.5 | 26.9 | 32.2 | 37.5 |
Table 2 operational condition
| Numbering | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Stock oil | A | B | C |
| The hydrogen dividing potential drop, MPa | 6.4 | 6.4 | 6.4 |
| Temperature of reaction, ℃ | 355 | 350/360 | 360 |
| Volume space velocity during liquid, h -1 | 3.0 | 2.1 | 2.5 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 500 | 700 | 500 |
Table 3 diesel product character
| Numbering | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Density (20 ℃), g/cm 3 | 0.8731 | 0.8365 | 0.8560 |
| Sulphur content, μ g/g | 50 | 22 | 45 |
| Nitrogen content, μ g/g | 5 | ＜1 | 4 |
| The bromine valency, gBr/100g | 0.6 | - | 0.5 |
| C, heavy % | 87.66 | - | 87.74 |
| H, heavy % | 12.14 | - | 12.18 |
| Cetane value | 38.4 | 42.6 | 45.6 |
| Cetane value improves | 13.9 | 15.7 | 13.4 |
| Diesel yield, heavy % | ＞98 | ＞95 | ＞95 |
Table 4 Comparative Examples 1 diesel product character
| Numbering | |
| Density (20 ℃), g/cm 3 | 0.8470 |
| Sulphur content, μ g/g | 60 |
| Nitrogen content, μ g/g | 10 |
| The bromine valency, gBr/100g | 0.5 |
| Cetane value | 48.5 |
| Cetane value improves | 11.0 |
| Diesel yield, heavy % | 87 |
Claims (8)
1. a method of hydrotreating that improves cetane number of secondary processing diesel oil, secondary processing diesel oil mixes with vegetables oil and/or animal grease, its mixing raw material is under the existence of hydrogen, with Hydrobon catalyst, contact, at 300～450 ℃ of average reaction temperature, hydrogen dividing potential drop 3.2～8.0MPa, volume space velocity 2.1～6.0h
-1, hydrogen to oil volume ratio 300～800Nm
3/ m
3condition under carry out hydrogenation reaction, its reaction effluent is through cooling, obtain diesel product after separation and fractionation, take mixing raw material as benchmark, by weight, described vegetables oil and/or the animal grease ratio in mixing raw material is 5～35%, described Hydrobon catalyst, take catalyzer as benchmark, it consists of: the heavy % of nickel oxide 1～10, molybdenum oxide and Tungsten oxide 99.999 sum are 10～50 heavy %, the heavy % of fluorine 1～10, the heavy % of phosphorus oxide 0.5～8, surplus is silica-alumina, take described carrier as benchmark, the content of the silicon oxide in silica-alumina is 2～45 heavy %, the content of aluminum oxide is 55～98 heavy %,
The upstream of described Hydrobon catalyst is filled with the hydrogenation protecting agent, take integer catalyzer as benchmark, and by volume, the filling ratio of described hydrogenation protecting agent is 1～30%;
Described hydrogenation protecting agent is that in VIB and VIII family, at least one base metal loads on the catalyzer on unformed aluminum oxide and/or silica-alumina supports, and its pore volume is 0.5-1.0ml/g, and specific surface area is 120-220m
2/ g.
2. in accordance with the method for claim 1, it is characterized in that, in described mixing raw material, take mixing raw material as benchmark, by weight, described vegetables oil and/or the animal grease ratio in mixing raw material is 5～30%.
3. in accordance with the method for claim 1, it is characterized in that, the boiling spread of described mixing raw material is 180～700 ℃.
4. in accordance with the method for claim 1, it is characterized in that, described secondary processing diesel oil is selected from one or more in catalytic cracking diesel oil, coker gas oil, catalytic pyrolysis diesel oil, visbreaking diesel oil, thermo-cracking diesel oil, direct liquefying diesel oil of coal.
5. in accordance with the method for claim 1, it is characterized in that described vegetables oil is one or more that are selected from plam oil, soybean oil, rapeseed oil, Oleum Gossypii semen, Semen Maydis oil, Rice pollard oil, sunflower oil, peanut oil, Viscotrol C, sesame oil, Fructus Zanthoxyli oil, tea oil, Oleum Cocois, sweet oil, coptis wood oil, tung oil, rosin oil, Chinese vegetable tallow, described animal grease is selected from one or more in lard, butter, sheep oil, fish oil.
6. in accordance with the method for claim 1, it is characterized in that described mixing raw material is at 330～380 ℃ of average reaction temperature, hydrogen dividing potential drop 4.0～6.4MPa, volume space velocity 2.1～4.0h
-1, hydrogen to oil volume ratio 400～600Nm
3/ m
3condition under carry out hydrogenation reaction.
7. in accordance with the method for claim 1, it is characterized in that the downstream of described Hydrobon catalyst also is filled with catalyst for hydro-upgrading, take integer catalyzer as benchmark, by volume, the filling ratio of described hydrogenation protecting agent is 1～30%.
8. in accordance with the method for claim 7, it is characterized in that described catalyst for hydro-upgrading contains a kind of carrier and loads on molybdenum and/or tungsten and nickel and/or the cobalt on this carrier, in oxide compound and take the catalyzer total amount as benchmark, the content of molybdenum and/or tungsten is 10～35 heavy %, the heavy % of content 1～15 of nickel and/or cobalt, this carrier is comprised of aluminum oxide and zeolite, and the weight ratio of aluminum oxide and zeolite is 90: 10～50: 50.
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| CA2982885C (en) * | 2015-04-27 | 2023-05-02 | Shell Internationale Research Maatschappij B.V. | Conversion of biomass or residual waste material to biofuels |
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| US5705722A (en) * | 1994-06-30 | 1998-01-06 | Natural Resources Canada | Conversion of biomass feedstock to diesel fuel additive |
| CN101029245A (en) * | 2007-04-13 | 2007-09-05 | 清华大学 | Production of biological diesel oil by integrated hydrogenation |
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|---|---|---|---|---|
| US5705722A (en) * | 1994-06-30 | 1998-01-06 | Natural Resources Canada | Conversion of biomass feedstock to diesel fuel additive |
| CN101029245A (en) * | 2007-04-13 | 2007-09-05 | 清华大学 | Production of biological diesel oil by integrated hydrogenation |
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| 植物油加氢制备高十六烷值柴油组分研究进展;赵阳 等;《化工进展》;20071025;第26卷(第10期);1391-1394 * |
| 赵阳 等.植物油加氢制备高十六烷值柴油组分研究进展.《化工进展》.2007,第26卷(第10期),1391-1394. |
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