CN103102904B - Two-stage hydrogenation method for producing high quality low freezing point motor fuel from biological oil - Google Patents
Two-stage hydrogenation method for producing high quality low freezing point motor fuel from biological oil Download PDFInfo
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- CN103102904B CN103102904B CN201110353635.6A CN201110353635A CN103102904B CN 103102904 B CN103102904 B CN 103102904B CN 201110353635 A CN201110353635 A CN 201110353635A CN 103102904 B CN103102904 B CN 103102904B
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Abstract
The present invention relates to a two-stage hydrogenation method for producing a high quality low freezing point motor fuel from a biological oil. The method is characterized in that a biological oil is adopted as a raw material oil; under a hydrogenation condition, the raw material oil and hydrogen are mixed, and pass through a first stage hydrogenation reaction zone; hydrogen-rich gas separated from a stream generated through hydrogenation is recycled at the first stage; the separated liquid enters a second stage hydrogenation modification reaction zone; and sub-hydrogen gas separated from the oil generated through second stage hydrogenation is recycled at the second stage, and the separated liquid product is subjected to fractionation to obtain naphtha and a low freezing point motor fuel, wherein hydrogenation activity components of the hydrogenation catalyst used at the first stage are reduction state Pt and/or Pd, and hydrogenation activity components of the hydrogenation catalyst used at the second stage are one or a plurality of materials selected from sulfurization state W, Mo, Ni and Co under a reaction state. Compared with the method in the prior art, the method of the present invention has the following advantages that: a low freezing point motor fuel can be produced, activity stability of the catalyst can be ensured, and stable and long period device operation can be ensured.
Description
Technical field
The present invention relates to a kind of method of hydrotreating, particularly a kind of is stock oil with bio-oil, the two-stage method method of hydrotreating of direct production high-grade low-freezing point automotive fuel.
Background technology
The energy in current global range is mainly derived from fossil energy, 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 produce a large amount of light clean fuel, these increase new oil substitutes while all requiring to improve existing oil Refining Technologies, produce satisfactory product with minimum cost.
Bio-oil, as renewable resources, obtains the extensive attention in the world, and each research unit and enterprise are all making great efforts to carry out its research as clean energy.The method production biofuel (being generally fatty acid methyl ester) utilizing transesterify has been proven technique, but because fatty acid methyl ester oxygen level is high, although many countries and regions have put into effect the standard of biofuel successively, and are not suitable for all oil engines.Bio-oil produces automotive fuel by the method for hydrogenation, and all remove by oxygen or partly remove the product produced and meet automotive fuel standard, this method directly can meet the requirement of existing market.
Existing animal-plant oil hydrogenation method produces 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 vegetables oil hydroconversion process, adopt coker naphtha, diesel oil distillate (straight-run diesel oil, LCO and coker gas oil), the petroleum hydrocarbon cuts such as wax oil cut and bio-oil are mixed into hydrogenation catalyst bed, produce diesel product or preparing ethylene by steam cracking raw material etc.US5705722 discloses the diesel oil blending component producing diesel oil distillate scope containing the vegetables oil such as unsaturated fatty acids, fat and animal oil mixing back end hydrogenation.
EP1741767 and EP1741768 discloses a kind of method of producing diesel oil distillate with animal-plant oil, be mainly animal-plant oil first through hydrotreatment, then by isomerization catalyst bed layer, obtain low freezing point diesel fuel component, but owing to generating water in hydroprocessing processes, cause very adverse influence to isomerization catalyst, device can not long-period stable operation.
Comprise in the bio-oil hydrogenation process of aforesaid method, one of subject matter run into is that bed carbon distribution causes shorten running period, needs more catalyst changeout of often stopping work.Particularly independent with bio-oil be raw material or bio-oil blending ratio higher time, the running period of hydrogenation catalyst is more subject to obvious impact.
In prior art, bio-oil hydrogenation produces the method for automotive fuel, the petroleum fractions hybrid process of general needs and larger proportion, otherwise can not running period be ensured, or directly by hydrofining-catalyst for hydro-upgrading bed, the component poor stability of cracking catalyst activity.The present invention is by optimizing the grating technology and operational condition that use catalyzer, first paragraph hydrofining (noble metal hydrogenation catalyst of grating), second segment hydro-upgrading, it can be directly raw material production high-grade low-freezing point automotive fuel with bio-oil, solving bio-oil hydrogenation unit can not the problem of long period steady running, significantly can reduce the condensation point of diesel oil distillate simultaneously.
Summary of the invention
For the deficiencies in the prior art, the invention provides the two-stage method method of hydrotreating that a kind of bio-oil produces high-grade low-freezing point automotive fuel, independent is stock oil with bio-oil, first paragraph uses noble metal catalyst, second segment uses sulphided state catalyst for hydro-upgrading, the method of the low condensation point automotive fuel of direct production under the condition of hydrogenation, can direct production super low sulfur, low density, low freezing point diesel fuel be in harmonious proportion product, the situation that diesel product can not be occurred biofuel that conventional animal-plant oil obtains is gone mouldy, hydrogenation process is stablized, and running period is long.
The two-stage method method of hydrotreating that a kind of bio-oil of the present invention produces high-grade low-freezing point automotive fuel comprises following content:
A one or more in () bio-oil are stock oil;
B () is under Hydroprocessing conditions, stock oil and hydrogen are by first paragraph reaction zone, first paragraph reaction zone comprises the hydrogenation catalyst bed that at least two hydrogenation active component content raise successively, first stock oil and hydrogen pass through the low beds of hydrogenation active component content, then the high beds of hydrogenation active component content is passed through, under response behaviour, hydrogenation active component is Pt and/or Pd of reduction-state;
C () first paragraph reaction zone hydrogenation effluent is separated into gas phase and liquid phase, recycle at first paragraph after gas-phase dehydration process, the second segment reaction zone using catalyst for hydro-upgrading is entered after liquid phase mixes with circulation gas, under response behaviour, the active metal component of catalyst for hydro-upgrading is one or more in W, Mo, Ni and Co of sulphided state;
D gas phase that () second segment reaction zone generates logistics recycles at second segment, and liquid phase fractionation in separation column that second segment reaction zone generates logistics obtains petroleum naphtha and low freezing point diesel fuel;
E () supplements S-contained substance in second segment reaction mass, to maintain hydrogen sulfide content in circulation gas.
In the inventive method step (a), the bio-oil used 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, sunflower seed oil and rice bran wet goods, and animal grease comprises one or more in butter, lard, sheep oil and fish oil etc.
In the inventive method step (b), the Hydroprocessing conditions of first paragraph reaction zone 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
-1~ 6.0h
-1, average reaction temperature 180 DEG C ~ 465 DEG C; Preferred operational condition is reaction pressure 3.0MPa ~ 18.0MPa, hydrogen to oil volume ratio 300:1 ~ 2500:1, volume space velocity 0.2h
-1~ 4.0h
-1, average reaction temperature 200 DEG C ~ 445 DEG C.
In the inventive method step (b), first paragraph reaction zone beds generally can arrange 2 ~ 5, in the beds that first reaction mass passes through, in the element of precious metals pt and/or Pd, the content of noble metal hydrogenation active ingredient is 0.01% ~ 0.50%, the hydrogenation catalyst that first reaction mass passes through accounts for 10% ~ 80% of all hydrogenation catalyst volumes in first paragraph reaction zone, and preferably 20% ~ 70%, best 30% ~ 60%.The hydrogenation active component of the downstream catalyst that reaction mass passes through increases by 0.05 ~ 3.0 percentage point in element quality than adjacent upstream catalyzer, preferably increases by 0.1 ~ 1.0 percentage point.The carrier of hydrogenation catalyst is generally aluminum oxide, amorphous silicon aluminium, silicon oxide, titanium oxide etc., can contain other auxiliary agent, as P, Si, B, Ti, Zr etc. simultaneously.Can commercial catalyst be adopted, also can by the existing method preparation in this area.Noble metal catalyst such as Fushun Petrochemical Research Institute (FRIPP) develops HDO-18 catalyzer, also can by described method preparations such as CN00123141.3.
In the inventive method step (b), catalyzer uses hydrogen 200 DEG C ~ 500 DEG C temperature before use, reduces under preferably 220 DEG C ~ 450 DEG C conditions.Whenever forbid in first paragraph system, inject sulfur-bearing, nitrogenous medium, avoid poisoning of catalyst.
In the inventive method step (c), the Hydroprocessing conditions of second segment reaction zone is generally reaction pressure 3.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.3h
-1~ 6.0h
-1, average reaction temperature 180 DEG C ~ 465 DEG C; Preferred operational condition is reaction pressure 3.0MPa ~ 18.0MPa, hydrogen to oil volume ratio 300:1 ~ 2500:1, volume space velocity 0.4h
-1~ 4.0h
-1, average reaction temperature 200 DEG C ~ 445 DEG C.First paragraph reaction zone hydrogenation effluent does not need cooling to carry out gas-liquid separation, and the water that reaction generates enters in gas phase.The working pressure of second segment reaction zone can be identical with first paragraph, also can be different.
In the inventive method step (c), the catalyst for hydro-upgrading of second segment reaction zone has isomery function, as containing beta-molecular sieve, and the components such as SAPO-11 molecular sieve, SAPO-41, NU-10 molecular sieve or ZSM-22 molecular sieve.The hydrogenation active metals component of catalyst for hydro-upgrading is generally 10% ~ 40% with the weight content of oxide basis, and the weight content of molecular sieve in catalyst for hydro-upgrading is generally 5% ~ 60%.The commercial catalysts that second segment reaction zone uses mainly contains, as FC-14, FC-16, FC-20 etc. that Fushun Petrochemical Research Institute (FRIPP) develops.
In the inventive method step (c), second segment reaction zone hydrogenation active component is the catalyzer of oxidation state, carries out conventional sulfidizing before the use, makes hydrogenation active component be converted into sulphided state, or use the catalyzer that ex situ presulfiding is good.
The sulfur-containing medium supplemented in reaction mass (optimum is dosed in the liquid phase feeding of second segment reaction zone) in the inventive method step (e) can be the compound of sulfur-bearing, as DMDS, CS
2deng, also can be the oil light-end products of sulfur-bearing, as the boat coal, diesel oil etc. of sulfur-bearing.Supplementing by sulphur, can ensure that the hydrogen sulfide content in circulation gas is not less than 0.005v%, preferred 0.01v% ~ 2.0v%.
Accompanying drawing explanation
Fig. 1 is the two-stage method method of hydrotreating principle flow chart that bio-oil of the present invention produces high-grade low-freezing point automotive fuel.
Fig. 2 is the another one principle flow chart that bio-oil of the present invention produces the two-stage method method of hydrotreating of high-grade low-freezing point automotive fuel.
Embodiment
Method of the present invention is specific as follows: with the mixing oil of one or more in bio-oil for stock oil, under Hydroprocessing conditions, stock oil and hydrogen are by comprising the first paragraph hydroconversion reaction zone of at least two kinds of hydrogenation catalysts, the hydrogenated oil obtained is separated in high-pressure separator (abbreviation high score) gas obtained and recycles at first paragraph, the liquid distillate obtained and hydrogen are mixed into the second segment reaction zone comprising and have isomery performance catalyst for hydro-upgrading, obtain hydro-upgrading logistics to be separated in high-pressure separator (abbreviation high score) gas obtained and to recycle at second segment, the liquid fractionation obtained obtains following products: gas, petroleum naphtha, one or more in diesel oil, if improve the character of diesel product further or extend the cycle of operation, also consider, at first paragraph, a part of diesel oil and unconverted oil are looped back first paragraph reactive system.The bio-oil that embodiment uses is commercially available prod, uses front filtering solid impurity.
Particular case of the present invention is further illustrated below by embodiment.
The main composition of table 1 hydrogenation catalyst and character.
| Catalyzer | Catalyzer 1 | Catalyzer 2 | Catalyzer 3 | Modifying catalyst |
| Catalyzer forms | ? | ? | ? | ? |
| Pt，wt% | 0.4 | 1.2 | 0.05 | ? |
| Pd，wt% | 0.1 | ? | 0.1 | ? |
| MoO 3，wt% | ? | ? | ? | 16.2 |
| NiO，wt% | ? | ? | ? | 2.4 |
| Beta-molecular sieve, wt% | ? | ? | ? | 15.0 |
| 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 | 0.33 | 0.32 | 0.35 | 0.34 |
Table 2 embodiment processing condition and test-results.
| First paragraph reaction zone processing condition | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Catalyzer | Catalyzer 1/ catalyzer 2 | Catalyzer 1/ catalyzer 2 | Catalyzer 3/ catalyzer 1/ catalyzer 2 |
| Catalyst volume ratio | 15:85 | 40:60 | 30：30：40 |
| Stock oil | Oleum Gossypii semen | Soybean oil | Soybean oil |
| Reaction pressure, MPa | 18.0 | 8.0 | 4.0 |
| Entrance hydrogen to oil volume ratio | 1000:1 | 1000:1 | 1000:1 |
| Cumulative volume air speed, h -1 | 1.5 | 0.7 | 0.4 |
| Average reaction temperature, DEG C | 300 | 220 | 150 |
| Second segment reaction zone processing condition | ? | ? | ? |
| Catalyzer | Modifying catalyst | Modifying catalyst | Modifying catalyst |
| Reaction pressure, MPa | 18.0 | 8.0 | 4.0 |
| Entrance hydrogen to oil volume ratio | 1500:1 | 500:1 | 800:1 |
| Volume space velocity, h -1 | 1.5 | 3.5 | 2.2 |
| Average reaction temperature, DEG C | 280 | 310 | 330 |
| Sulfur-containing medium | DMDS | DMDS | CS 2 |
| Hydrogen sulfide content in second segment circulation gas, μ L/L | 50 | 10000 | 500 |
| Diesel product | ? | ? | ? |
| Density, g/cm 3 | 0.782 | 0.781 | 0.780 |
| Sulphur content, μ g/g | <1 | <1 | <1 |
| Condensation point, DEG C | -10 | -20 | -25 |
| Cetane value | >80 | >80 | >80 |
Table 3 embodiment processing condition and test-results.
| First paragraph reaction zone processing condition | Embodiment 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Catalyzer | Catalyzer 1/ catalyzer 2 | Catalyzer 2/ modifying catalyst | Catalyzer 2/ modifying catalyst | Catalyzer 2/ modifying catalyst |
| Catalyst volume ratio | 40:60 | ? | ? | ? |
| 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 |
| Entrance hydrogen to oil volume ratio | 1000:1 | 1000:1 | 1000:1 | 1000:1 |
| Cumulative volume air speed, h -1 | 0.5 | 0.4 | 0.4 | 0.4 |
| Average reaction temperature, DEG C | 310 | 310 | 310 | 320 |
| Second segment reaction zone processing condition | ? | — | — | — |
| Catalyzer | Modifying catalyst | ? | ? | ? |
| Reaction pressure, MPa | 10.0 | ? | ? | ? |
| Entrance hydrogen to oil volume ratio | 1000:1 | ? | ? | ? |
| Volume space velocity, h -1 | 2.0 | ? | ? | ? |
| Average reaction temperature, DEG C | 310 | ? | ? | ? |
| Sulfur-containing medium | DMDS | ? | ? | ? |
| Hydrogen sulfide content in second segment circulation gas, μ L/L | 200 | ? | ? | ? |
| Runtime, h | 1000 | 200 | 400 | 600 |
| Pressure Drop, MPa | 0 | 0.1 | 0.3 | 0.6 |
| Diesel product | ? | ? | ? | ? |
| Density, g/cm 3 | 0.786 | 0.787 | 0.810 | 0.862 |
| Sulphur content, μ g/g | <5 | <5 | <5 | <5 |
| Condensation point, DEG C | -20 | -19 | 0 | 12 |
| Cetane value | >80 | >80 | 78 | 70 |
Comparative example catalyzer 2 consumption is identical with the total consumption of embodiment 4 catalyzer 1 and catalyzer 2, and comparative example modifying catalyst consumption is identical with embodiment 4 modifying catalyst consumption.
As can be seen from embodiment, bio-oil can direct production high-grade low-freezing point diesel product by the method for hydrotreating of this technology, or fine-quality diesel oil blending component, and can realize long-period stable operation.
Claims (11)
1. bio-oil produces a two-stage method method of hydrotreating for high-grade low-freezing point automotive fuel, it is characterized in that comprising following content:
A one or more in () bio-oil are stock oil;
B () is under Hydroprocessing conditions, stock oil and hydrogen are by first paragraph reaction zone, first paragraph reaction zone comprises the hydrogenation catalyst bed that at least two hydrogenation active component content raise successively, first stock oil and hydrogen pass through the low beds of hydrogenation active component content, then the high beds of hydrogenation active component content is passed through, under response behaviour, hydrogenation active component is Pt and/or Pd of reduction-state, in the beds that first reaction mass passes through, in the element quality of precious metals pt and/or Pd, the content of noble metal hydrogenation active ingredient is 0.01% ~ 0.50%, the hydrogenation active component of the downstream catalyst that reaction mass passes through increases by 0.05 ~ 3.0 percentage point in element quality than adjacent upstream catalyzer,
C () first paragraph reaction zone hydrogenation effluent is separated into gas phase and liquid phase, recycle at first paragraph after gas-phase dehydration process, the second segment reaction zone using catalyst for hydro-upgrading is entered after liquid phase mixes with circulation gas, under response behaviour, the active metal component of catalyst for hydro-upgrading is one or more in W, Mo, Ni and Co of sulphided state;
D gas phase that () second segment reaction zone generates logistics recycles at second segment, and liquid phase fractionation in separation column that second segment reaction zone generates logistics obtains petroleum naphtha and low freezing point diesel fuel;
E () supplements S-contained substance in second segment reaction mass, to maintain hydrogen sulfide content in circulation gas.
2. in accordance with the method for claim 1, it is characterized in that: in 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 step (b), the reaction pressure of first paragraph reaction zone is 3.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.1h
-1~ 6.0h
-1, average reaction temperature 180 DEG C ~ 465 DEG C.
4. in accordance with the method for claim 1, it is characterized in that: in step (b), the reaction pressure 3.0MPa ~ 18.0MPa of first paragraph reaction zone, hydrogen to oil volume ratio 300:1 ~ 2500:1, volume space velocity 0.2h
-1~ 4.0h
-1, average reaction temperature 200 DEG C ~ 445 DEG C.
5. according to the method described in claim 1 or 3, it is characterized in that: in step (b), first paragraph reaction zone beds arranges 2 ~ 5, and the hydrogenation catalyst that first reaction mass passes through accounts for 10% ~ 80% of all hydrogenation catalyst volumes in first paragraph reaction zone.
6. in accordance with the method for claim 5, it is characterized in that: in step (b) first paragraph reaction zone, the hydrogenation catalyst that first reaction mass passes through accounts for 20% ~ 70% of all hydrogenation catalyst volumes in first paragraph reaction zone, and the hydrogenation active component of the downstream catalyst that reaction mass passes through increases by 0.1 ~ 1.0 percentage point in element quality than adjacent upstream catalyzer.
7. in accordance with the method for claim 1, it is characterized in that: in step (c), the reaction pressure of second segment reaction zone is 3.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.3h
-1~ 6.0h
-1, average reaction temperature 180 DEG C ~ 465 DEG C.
8. in accordance with the method for claim 7, it is characterized in that: in step (c), the reaction pressure of second segment reaction zone is 3.0MPa ~ 18.0MPa hydrogen to oil volume ratio is 300:1 ~ 2500:1, and volume space velocity is 0.4h
-1~ 4.0h
-1, average reaction temperature is 200 DEG C ~ 445 DEG C.
9. in accordance with the method for claim 1, it is characterized in that: in step (c), the catalyst for hydro-upgrading of second segment reaction zone has isomery function, catalyst for hydro-upgrading contains beta-molecular sieve, SAPO-11 molecular sieve, SAPO-41, NU-10 molecular sieve or ZSM-22 molecular sieve component, the hydrogenation active metals component of catalyst for hydro-upgrading with the weight content of oxide basis for 10% ~ 40%.
10. in accordance with the method for claim 1, it is characterized in that: the sulfur-containing medium supplemented in the reaction mass of second segment reaction zone is the compound of sulfur-bearing, or the oil light-end products of sulfur-bearing.
11., according to the method described in claim 1 or 10, is characterized in that: in circulation gas, hydrogen sulfide content is not less than 0.005v%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029245A (en) * | 2007-04-13 | 2007-09-05 | 清华大学 | Production of biological diesel oil by integrated hydrogenation |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101617029A (en) * | 2007-02-20 | 2009-12-30 | 国际壳牌研究有限公司 | Produce the method for paraffinic hydrocarbons |
| CN101029245A (en) * | 2007-04-13 | 2007-09-05 | 清华大学 | Production of biological diesel oil by integrated hydrogenation |
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