CN102911699A - Hydrogenation method for producing motor fuels by using biological oil and fat - Google Patents
Hydrogenation method for producing motor fuels by using biological oil and fat Download PDFInfo
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- CN102911699A CN102911699A CN2011102175736A CN201110217573A CN102911699A CN 102911699 A CN102911699 A CN 102911699A CN 2011102175736 A CN2011102175736 A CN 2011102175736A CN 201110217573 A CN201110217573 A CN 201110217573A CN 102911699 A CN102911699 A CN 102911699A
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Abstract
The invention discloses a hydrogenation method for producing motor fuels by using biological oil and fat. The method comprises the steps of (a) selecting one or more of the biological oil and fat as raw oil; (b) passing the raw oil and hydrogen successively through at least two reduced hydrogenation catalyst layers which has increasing content of a hydrogenation active component in sequence, wherein the raw oil and hydrogen are introduced in from the bottom of a reactor, reaction materials firstly pass through the reduced hydrogenation catalyst layer with low content of the hydrogenation active component, and then pass through the reduced hydrogenation catalyst layer with high content of the hydrogenation active component; and in a reacting state, the hydrogenation active component is one or more of sulfide W, Mo, Ni and Co; (c) separating hydrogenation reaction products; and (d) supplementing sulfur-containing substances in the reaction material flow to maintain the content of hydrogen sulfide in a circulation gas. The method provided by the invention can guarantee that a hydrogenation apparatus of the biological oil and fat runs stably in a long period.
Description
Technical field
The invention belongs to the production method of renewable energy source, particularly a kind of take bio-oil as stock oil, the method for hydrotreating of direct production automotive fuel.
Background technology
The energy in the global range is mainly derived from fossil energy at present, and its PetroChina Company Limited. is the main source of automotive fuel.Oil belongs to Nonrenewable energy resources, not only resource is day by day exhausted, and heaviness and in poor quality aggravation, and world economy sustainable development, environmental regulation increasingly stringent need to be produced a large amount of light clean fuels, increase new oil substitutes when these all require existing oil Refining Technologies improved, produce satisfactory product with minimum cost.
Bio-oil obtains the extensive attention in the world as renewable resources, and each research unit and enterprise are all making great efforts to carry out it as the research of clean energy.Utilizing the method production biofuel (being generally fatty acid methyl ester) of transesterify has been proven technique, but because the fatty acid methyl ester oxygen level is high, although many countries and regions have been put into effect the standard of biofuel successively, and be not suitable for all oil engines.Bio-oil is produced automotive fuel by the method for hydrogenation, and soon oxygen is all removed or partly removed and produce the product that meets the automotive fuel standard, and this method can directly satisfy the requirement of existing market.
Existing animal-plant oil 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), the petroleum hydrocarbon cut such as wax oil cut and bio-oil are mixed into the hydrogenation catalyst bed, produce diesel product or preparing ethylene by steam cracking raw material 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 generating water in the hydrotreatment process, isomerization catalyst is caused very adverse influence, and device can not long-period stable operation.
Comprise that one of subject matter that runs into is the less stable of hydrogenation unit in the bio-oil hydrogenation process of aforesaid method, catalyzer is easy to carbon deposit, the pressure drop of reactor is risen very fast, catalyst deactivation speed is fast, and running period is shorter, and needing often stops work changes or regenerated catalyst.Particularly separately take bio-oil as raw material or bio-oil blending ratio when higher, more be subject to obvious impact the running period of hydrogenation catalyst, can't satisfy the requirement of industrial application.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of bio-oil and produce the method for hydrotreating of automotive fuel, can be separately take bio-oil as stock oil, the method of direct production automotive fuel under the condition of hydrogenation, reduce reactor pressure decrease, the high-quality diesel oil of direct production is in harmonious proportion product, makes diesel product that the situation that biofuel that conventional animal-plant oil makes is gone mouldy can not occur, hydrogenation process is stable, and running period is long.
The method of hydrotreating that bio-oil of the present invention is produced automotive fuel comprises following content:
(a) one or more in the bio-oil are stock oil;
(b) under the hydroprocessing condition, the hydrogenation catalyst bed that stock oil and hydrogen raise successively by at least two hydrogenation activity component concentrations, stock oil and hydrogen enter from reactor bottom, reaction mass is at first by the low beds of hydrogenation activity component concentration, then by the high beds of hydrogenation activity component concentration, under response behaviour, the hydrogenation activity component is among W, Mo, Ni and the Co of sulphided state one or more;
(c) effluent after the hydrogenation reaction is discharged from reactor head, then is separated into gas phase and liquid phase, and gas phase recycles, and liquid phase enters separation column;
(d) liquid phase fractionation in separation column obtains petroleum naphtha and diesel oil;
(e) in reactant flow, replenish S-contained substance, to keep hydrogen sulfide content in the circulation gas.
The bio-oil that the inventive method is used can comprise vegetables oil and/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, sunflower seed oil and the rice bran wet goods, and animal grease comprises one or more in butter, lard, sheep oil and the fish oil etc.But also other raw material of mixing portion in the bio-oil, such as petroleum fractions, liquefied coal coil, coal tar, shale wet goods, blending ratio is determined on demand, is generally (weight) below 50%.
The hydroprocessing condition is generally reaction pressure 3.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.1h during liquid
-1~ 6.0h
-1, 180 ℃ ~ 465 ℃ of average reaction temperature; Preferred operational condition is reaction pressure 4.0MPa ~ 18.0MPa, hydrogen to oil volume ratio 300:1 ~ 2500:1, volume space velocity 0.2h during liquid
-1~ 4.0h
-1, 200 ℃ ~ 445 ℃ of average reaction temperature.
In the hydrogenation catalyst of the beds that the hydrogenation activity component concentration that reaction mass at first passes through is low, the hydrogenation activity component is take the weight content of oxide compound as 3%～10%, the hydrogenation catalyst of the beds that the hydrogenation activity component concentration that reaction mass at first passes through is low accounts for 10% ~ 80% of all hydrogenation catalyst volumes, preferred 20% ~ 70%, best 30% ~ 60%.The hydrogenation activity component of the hydrogenation catalyst of the beds that the downstream hydrogenation activity component concentration that reaction mass passes through is high increases by 3～25 percentage points in oxide weight than adjacent upstream catalyzer, preferably increases by 5 ~ 20 percentage points.Beds generally can arrange 2 ~ 5.Above-mentioned upstream and downstream refers to according to the mobile orientation determination of reaction mass, opposite with the upper-lower position of catalyzer in reactor, the beds that is reactor lower part is the upstream position of reaction mass, the beds on reactor top is the downstream position of reaction mass, adopt the upwards operating method of mobile upflowing (reaction mass enters from reactor bottom, discharges from reactor head) of reaction mass because be.
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.Commercially available hydrogenation catalyst can be oxidation state, also can be sulphided state, when adopting the oxidation state hydrogenation catalyst, carries out conventional sulfidizing before using, and makes the hydrogenation activity component be converted into sulphided state.
Commercial hydrogenation catalyst mainly contains, such as 3926 of Fushun Petrochemical Research Institute (FRIPP) development, 3936, CH-20, FF-14, FF-18, FF-24, FF-26, FF-36, FH-98, FH-UDS, the hydrogenation catalysts such as FZC-41, the HR-416 of Inst Francais Du Petrole, the hydrogenation catalysts such as HR-448, the ICR174 of CLG company, ICR178, ICR 179 hydrogenation catalysts such as grade, Uop Inc. is newly developed HC-P, HC-K UF-210/220, the TK-525 of Topsor company, TK-555, the hydrogenation catalysts such as TK-557, the KF-752 of AKZO company, KF-840, KF-848, KF-901, the hydrogenation catalysts such as KF-907.
In the inventive method, when low conversion rate in 100% the time, can obtain the part unconverted oil in step (d) fraction products, unconverted oil and part diesel oil can loop back reactive system, the material of circulation is fresh feed weight of oil≤50%, be preferably fresh feed oil≤35%, fresh feed oil is the bio-oil raw material that does not mix with recycle stock.
The sulfur-containing medium that replenishes in the reaction mass can be the compound of sulfur-bearing, such as DMDS, and CS
2Deng, also can be the distillate of sulfur-bearing, such as the boat coal of sulfur-bearing, diesel oil etc.By replenishing of sulphur, can guarantee that the hydrogen sulfide content in the circulation gas is not less than 0.005v%, preferred 0.01v%～1.0v%.
The hydrogenator that the inventive method is used is the upflowing hydrogenator, upflowing hydrogenator top can arrange suitable gas-liquid separation space, pass through fluid level control device, gas phase is discharged from reactor head, liquid phase is discharged from the bottom, gas-liquid separation space of reactor head, the liquid phase of discharging can directly enter fractionating system, can save gas-liquid separator like this, takes full advantage of the space of hydrogenator.
The bio-oil hydrogenation is produced the method for automotive fuel in the prior art, and the catalyzer coking produces pressure drop in the reaction process, and obviously reduces the reactive behavior of catalyzer, can not guarantee running period.The present invention is by optimizing grating technology and the upflowing hydrotreatment operational condition of using catalyzer, can effectively reduce reactor pressure decrease, and the assurance hydrogenation catalyst is activity stabilized, directly take bio-oil as raw material production high-quality automotive fuel, solved the problem that the bio-oil hydrogenation unit can not the long period steady running.In addition, diesel oil distillate behind the partial reaction and unconverted oil are looped back hydrogenation reaction system, can further improve the stable operation of bio-oil hydrogenation unit.
Description of drawings
Fig. 1 is the method for hydrotreating principle flow chart that bio-oil of the present invention is produced automotive fuel.
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 hydrotreatment operational condition, stock oil 1 enters hydrotreating reactor 3 by the hydrotreatment reaction zone of at least two kinds of hydrogenation catalysts with hydrogen 2 from reactor bottom, the hydrotreatment that obtains generates oil 4 and is called for short high score at high-pressure separator 5() separate the gas 6 that obtains and recycle, also can go out system, the liquid 7 that obtains enters separation column 12 and obtains following products: gas 8, petroleum naphtha 9, in the diesel oil 10 one or more, if further improve the character of diesel product or prolong the cycle of operation, consider that also a part of diesel oil and unconverted oil 11(low conversion rate are in 100% the time) loop back reactive system.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.Comparative example 1 adopts conventional downflow system hydrotreatment operation.
The chief component of table 1 hydrotreating catalyst and character.
| Catalyzer | Catalyzer 1 | Catalyzer 2 | Catalyzer 3 | Catalyzer 4 |
| Catalyzer forms | ? | ? | ? | ? |
| MoO 3，wt% | 7.0 | 5.0 | 24.5 | 15.7 |
| NiO，wt% | 2.0 | / | 3.8 | 2.4 |
| CoO，wt% | / | 1.6 | / | / |
| Alumina supporter, wt% | Surplus | Surplus | Surplus | Surplus |
| The main character of catalyzer | ? | ? | ? | ? |
| Specific surface, m 2/g | >160 | >160 | >160 | >160 |
| Pore volume, ml/g | >0.30 | >0.30 | >0.30 | >0.30 |
Table 2 embodiment processing condition and test-results.
| Processing condition | Embodiment 1 | Embodiment 2 | |
Embodiment 4 |
| Catalyzer (pressing the mobile direction filling of reaction mass) | Catalyzer 1/ |
Catalyzer 2/ |
Catalyzer 2/ |
Catalyzer 1/ catalyzer 4/ |
| The catalyst volume ratio | 10:90 | 20:80 | 40:60 | 25：35：40 |
| Stock oil | Soybean oil | Rapeseed oil | Oleum Gossypii semen | Oleum Gossypii semen |
| Reaction pressure, MPa | 17.0 | 5.0 | 10.0 | 10.0 |
| The entrance hydrogen to oil volume ratio | 2000:1 | 300:1 | 1000:1 | 1000:1 |
| The cumulative volume air speed, h -1 | 2.0 | 1.8 | 0.5 | 0.5 |
| Average reaction temperature, ℃ | 370 | 365 | 320 | 320 |
| Sulfur-containing medium | DMDS | DMDS | CS 2 | CS 2 |
| Hydrogen sulfide content in the circulation gas, μ L/L | 60 | 10000 | 500 | 500 |
| Per pass conversion, quality % | 100 | 90 | 80 | 78 |
| Diesel product | ? | ? | ? | ? |
| Density, g/cm 3 | 0.787 | 0.795 | 0.788 | 0.795 |
| Sulphur content, μ g/g | <5 | <5 | <5 | <5 |
| Cetane value | >80 | >80 | >80 | >80 |
Table 3 embodiment processing condition and test-results.
| | Embodiment | 5 | Comparative example 1* | Comparative example 2* | Comparative example 3* |
| Catalyzer (pressing the mobile direction filling of reaction mass) | Catalyzer 2/ |
Catalyzer 2/ |
Catalyzer 3 | Catalyzer 3 | |
| The catalyst volume ratio | 60:40 | 60:40 | 100 | 100 | |
| Stock oil | Oleum Gossypii semen | Oleum Gossypii semen | Oleum Gossypii semen | Oleum Gossypii semen | |
| Reaction pressure, MPa | 10.0 | 10.0 | 10.0 | 10.0 | |
| The entrance hydrogen to oil volume ratio | 1000:1 | 1000:1 | 1000:1 | 1000:1 | |
| The cumulative volume air speed, h -1 | 0.5 | 0.5 | 0.5 | 0.5 | |
| Average reaction temperature, ℃ | 330 | 330 | 330 | 340 | |
| Sulfur-containing medium | CS 2 | CS 2 | CS 2 | CS 2 | |
| Hydrogen sulfide content in the circulation gas, μ L/L | 500 | 500 | 500 | 500 | |
| Runtime, h | 2500 | 1000 | 300 | 500 | |
| Per pass conversion, quality % | 100 | 80 | 60 | 40 | |
| Diesel product | ? | ? | ? | ? | |
| Density, g/cm 3 | 0.788 | 0.791 | 0.812 | 0.865 | |
| Sulphur content, μ g/g | <5 | <5 | <5 | <5 | |
| Cetane value | >80 | >80 | 78 | 70 |
* comparative example 1-3 is the operating method that gas and liquid flowing flows downward.
Can be found out by embodiment, the method for hydrotreating of bio-oil by present technique can the direct production diesel product, perhaps fine-quality diesel oil blending component, and can long-period stable operation.
Claims (10)
1. a bio-oil is produced the method for hydrotreating of automotive fuel, it is characterized in that comprising following process:
(a) one or more in the bio-oil are stock oil;
(b) under the hydroprocessing condition, the hydrogenation catalyst bed that stock oil and hydrogen raise successively by at least two hydrogenation activity component concentrations, stock oil and hydrogen enter from reactor bottom, reaction mass is at first by the low beds of hydrogenation activity component concentration, then by the high beds of hydrogenation activity component concentration, under response behaviour, the hydrogenation activity component is among W, Mo, Ni and the Co of sulphided state one or more;
(c) effluent after the hydrogenation reaction is discharged from reactor head, then is separated into gas phase and liquid phase, and gas phase recycles, and liquid phase enters separation column;
(d) liquid phase fractionation in separation column obtains petroleum naphtha and diesel oil;
(e) in reactant flow, replenish S-contained substance, to keep hydrogen sulfide content in the circulation gas.
2. in accordance with the method for claim 1, it is characterized in that: bio-oil comprises vegetables oil and/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, sunflower seed oil and the Rice pollard oil, and animal grease comprises one or more in butter, lard, sheep oil and the fish oil.
3. according to claim 1 or 2 described methods, it is characterized in that: mix in the bio-oil and add petroleum fractions, liquefied coal coil, coal tar or shale oil, by weight, mixing the content that adds petroleum fractions, liquefied coal coil, coal tar or shale oil is below 50%.
4. in accordance with the method for claim 1, it is characterized in that: the reaction pressure of hydroprocessing condition is 3.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.1h during liquid
-1~ 6.0h
-1, average reaction temperature is 180 ℃ ~ 465 ℃.
5. in accordance with the method for claim 1, it is characterized in that: the reaction pressure of hydroprocessing condition is 4.0MPa ~ 18.0MPa, and hydrogen to oil volume ratio is 300:1 ~ 2500:1, and volume space velocity is 0.2h during liquid
-1~ 4.0h
-1, average reaction temperature is 200 ℃ ~ 445 ℃.
6. in accordance with the method for claim 1, it is characterized in that: in the hydrogenation catalyst of the beds that the hydrogenation activity component concentration that reaction mass at first passes through is low, the hydrogenation activity component is take the weight content of oxide compound as 3%～10%, and the hydrogenation catalyst of the beds that the hydrogenation activity component concentration that reaction mass at first passes through is low accounts for 10% ~ 80% of all hydrogenation catalyst volumes.
7. according to claim 1 or 6 described methods, it is characterized in that: the hydrogenation catalyst of the beds that the hydrogenation activity component concentration that reaction mass at first passes through is low accounts for 20% ~ 70% of all hydrogenation catalyst volumes.
8. according to claim 1 or 6 described methods, it is characterized in that: the hydrogenation activity component of the hydrogenation catalyst of the beds that the downstream hydrogenation activity component concentration that reaction mass passes through is high increases by 3～25 percentage points in oxide weight than adjacent upstream catalyzer.
9. it is characterized in that in accordance with the method for claim 8: beds arranges 2 ~ 5.
10. in accordance with the method for claim 1, it is characterized in that: the sulfur-containing medium that replenishes in the reaction mass is the compound of sulfur-bearing, or the distillate of sulfur-bearing, guarantees that the hydrogen sulfide content in the circulation gas is not less than 0.005v%, is preferably 0.01v%～1.0v%.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009138144A (en) * | 2007-12-07 | 2009-06-25 | Nippon Oil Corp | Method for producing hydrocarbon 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 |
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2011
- 2011-08-01 CN CN2011102175736A patent/CN102911699A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101617029A (en) * | 2007-02-20 | 2009-12-30 | 国际壳牌研究有限公司 | Produce the method for paraffinic hydrocarbons |
| JP2009138144A (en) * | 2007-12-07 | 2009-06-25 | Nippon Oil Corp | Method for producing hydrocarbon oil |
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