CN103102918B - Two-stage hydrogenation method for producing solvent oil - Google Patents
Two-stage hydrogenation method for producing solvent oil Download PDFInfo
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Abstract
The present invention relates to a two-stage hydrogenation method for producing a solvent 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; the stream generated from hydrogenation is separated to obtain hydrogen-rich gas; the hydrogen-rich gas is recycled at the first stage; the separated liquid enters a second stage hydrocracking reaction zone; the sub-hydrogen gas separated from the oil generated through second stage hydrogenation is recycled at the second stage circulation; and the separated liquid product is subjected to fractionation to obtain various solvent oil products, wherein hydrogenation activity components of the hydrogenation catalyst used at the first stage are one or a plurality of materials selected from sulfurization state W, Mo, Ni and Co and hydrogenation activity components of the hydrogenation catalyst used at the second stage are one or a plurality of materials selected from reduction state W, Mo, Ni and Co under a reaction state. Compared to the method in the prior art, the two-stage hydrogenation method of the present invention has the following characteristics that: low aromatic hydrocarbon solvent oil production methods are increased, 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 solvent oil.
Background technology
World economy sustainable development, in current global range, the main source of Chemicals is fossil energy, wherein most importantly oil and coal.These two kinds of fossil energies all belong to Nonrenewable energy resources, not only resource is day by day exhausted, and heaviness and in poor quality aggravation, difficulty of processing and tooling cost increase gradually, new oil substitutes is found except carrying out existing oil Refining Technologies improving, produce satisfactory product with minimum cost, especially the development and utilization of renewable resources obtains paying attention to more and more widely.
Bio-oil is as renewable resources, and main composition is carbon, hydrogen and oxygen, very similar to the composition of alkane, alcohol, ether etc., 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 low freezing point diesel fuel cut with animal-plant oil.
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, and the main purpose product of these technology is automotive fuel.
Solvent oil is important petroleum products, and its added value is higher than fuel product, and particularly the added value of high-grade low aromatic solvent naphtha is higher.The low aromatic solvent naphtha raw materials for production of current top grade are limited (is generally only limitted to gasoline fraction or the kerosene(oil)fraction of paraffinic crude, or reforming raffinate oil etc.), owing to requiring aromaticity content lower (some solvent oil index request aromaticity content is lower than 0.1%), therefore need to adopt complicated processing route, condition is harsh, production cost is high, limits the production of high-grade low aromatic solvent naphtha.
In prior art, bio-oil usually passes through separately or produces the method for automotive fuel with the method for other petroleum products mixing back end hydrogenations.The present invention is by optimizing the grating technology and operational condition that use reduction-state hydrogenation catalyst, first paragraph hydrotreatment (sulfurized hydrogenation catalyst of grating), second segment hydrocracking (reduced form hydrocracking catalyst) can be directly raw material production low aromatic solvent naphtha with bio-oil.The present invention extends the raw material sources of high added value low aromatic solvent naphtha, and production cost is low, can improve added value of product further.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of two-stage method method of hydrotreating producing solvent oil, independent is stock oil with bio-oil, first paragraph uses the sulphided state hydrogenation catalyst of grating, second segment uses reduction-state hydrocracking catalyst, direct production solvent oil under the condition of hydrogenation, has hydrogenation process and stablizes, the features such as running period is long.
A kind of two-stage method method of hydrotreating producing solvent oil of the present invention 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 one or more in W, Mo, Ni and Co of sulphided 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, liquid phase enters the second segment reaction zone using hydrocracking catalyst after mixing with second segment reaction zone circulation gas, under response behaviour, the active metal component of hydrocracking catalyst is one or more in W, Mo, Ni and Co of reduction-state;
D gas phase that () second segment reaction zone generates logistics recycles in second segment reaction zone, and liquid phase fractionation in separation column that second segment reaction zone generates logistics obtains spirit fraction;
E () supplements S-contained substance in first paragraph reaction mass, to maintain hydrogen sulfide content in the circulation gas of first paragraph reaction zone.
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, hydrogenation active component with the weight content of oxide basis for 3% ~ 10%, the hydrogenation catalyst that first reaction mass passes through accounts for 10% ~ 80% of all hydrogenation catalyst volumes in first paragraph reaction zone, preferably 20% ~ 70%, best 30% ~ 60%.The hydrogenation active component content of the downstream catalyst that reaction mass passes through increases by 3 ~ 25 percentage points in oxide weight than adjacent upstream catalyzer, preferably increases by 5 ~ 20 percentage points.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.The business hydrogenation catalyst that first paragraph reaction zone uses mainly contains, as Fushun Petrochemical Research Institute (FRIPP) develop 3926, 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, hydrogenation catalyst such as ICR 179 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.First paragraph reaction zone hydrogenation effluent is separated can comprise fractionating system, also can not comprise fractionating system (only comprising Separate System of Water-jet).When comprising fractionating system, the middle runnings (i.e. diesel oil distillate) fractionating system fractionation obtained enters second segment reaction zone.
In the inventive method step (b), first paragraph 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.
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.The liquid phase entering second segment reaction zone can be the liquid phase material after the gas-liquid separation of first paragraph reaction zone, also can be the intermediate oil that the liquid phase material after the gas-liquid separation of first paragraph reaction zone obtains through separation column fractionation.
In the inventive method step (c), the hydrocracking catalyst of second segment reaction zone has cracking function, as containing the component such as Y zeolite and/or ZSM-5 molecular sieve.The hydrogenation active metals component of hydrocracking catalyst is generally 5% ~ 40% with the weight content of oxide basis.The weight content of molecular sieve component in hydrocracking catalyst is generally 5% ~ 60%.Other refractory inorganic oxides can be contained in hydrocracking catalyst simultaneously.Second segment reaction zone use commercial catalysts mainly contain, as Fushun Petrochemical Research Institute (FRIPP) develop 3971,3976, FC-12, FC-18, FC-24, FC-26, FC-32, FC-46, FC-50, FDW-1 etc.
In the inventive method step (c), second segment reaction zone 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 second segment system, inject sulfur-bearing, nitrogenous medium, avoid poisoning of catalyst.
In the inventive method step (d), the low aromatic solvent naphtha obtained is mixed solvent oil distillate, can continue fractionation according to the actual requirements and obtain vegetable oil extraction solvent, No. 90 solvent oils, No. 120 solvent oils, No. 200 solvent oils, D30, D40 etc. trade mark low aromatic solvent naphthas.Specifically specifically can determine according to the boiling range of mixed solvent oil.If there is unconverted oil, unconverted oil can go out system, also capable of circulation time reactive system.
The sulfur-containing medium supplemented in first paragraph reaction mass (optimum is dosed in the liquid phase feeding of first paragraph 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 petroleum naphtha, boat coal etc. of sulfur-bearing.Supplementing by sulphur, can ensure that the hydrogen sulfide content in the circulation gas of first paragraph reaction zone 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 the present invention produces solvent oil.
Fig. 2 is the another one principle flow chart that the present invention produces the two-stage method method of hydrotreating of solvent oil.
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 in first paragraph reaction zone, the liquid distillate obtained and hydrogen are mixed into the second segment reaction zone comprising and have cracking performance Nobel metal hydrogen cracking catalyst, obtain hydrocracking logistics to be separated in high-pressure separator (abbreviation high score) gas obtained and to recycle at second segment, the liquid fractionation obtained obtains all kinds of SOLVENTS oil production, also consider, at first paragraph, a part of middle runnings and unconverted oil are looped back first paragraph reaction zone.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 | Catalyzer 4 | Cracking catalyst |
| Catalyzer forms | |||||
| MoO 3，wt% | 3.9 | 8.0 | 13.6 | 24.9 | 22.4 |
| NiO，wt% | 1.2 | 2.8 | 3.7 | 3.5 | |
| CoO，wt% | 1.6 | ||||
| Y molecular sieve, wt% | 15.8 | ||||
| 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 | >0.30 | >0.30 | >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 4 | Catalyzer 1/ catalyzer 3 | Catalyzer 1/ catalyzer 2/ catalyzer 3 |
| Catalyst volume ratio | 20:80 | 30:70 | 15:35:50 |
| Stock oil | Peanut oil | Soybean oil | Viscotrol C |
| Reaction pressure, MPa | 15.0 | 8.0 | 6.0 |
| Entrance hydrogen to oil volume ratio | 1500:1 | 1000:1 | 1000:1 |
| Cumulative volume air speed, h -1 | 1.0 | 1.5 | 0.4 |
| Average reaction temperature, DEG C | 350 | 310 | 260 |
| Sulfur-containing medium | DMDS | DMDS | CS 2 |
| Hydrogen sulfide content in first paragraph circulation gas, μ L/L | 200 | 800 | 6000 |
| Second segment reaction zone processing condition | |||
| Catalyzer | Cracking catalyst | Cracking catalyst | Cracking catalyst |
| Reaction pressure, MPa | 15.0 | 16.0 | 6.0 |
| Entrance hydrogen to oil volume ratio | 2000:1 | 1000:1 | 700:1 |
| Volume space velocity, h -1 | 1.2 | 2.58 | 4.2 |
| Average reaction temperature, DEG C | 280 | 340 | 300 |
| Spirit fraction | |||
| Yield, quality % | 88 | 81 | 75 |
| Aromaticity content | Do not detect | Do not detect | Do not detect |
| Sulphur content, μ g/g | Do not detect | Do not detect | Do not detect |
| Boiling range scope, DEG C | 61～176 | 63～165 | 65～120 |
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 3 | Catalyzer 3 | Catalyzer 3 | Catalyzer 3 |
| 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 | 0.5 | 0.5 | 0.5 |
| Average reaction temperature, DEG C | 320 | 320 | 320 | 320 |
| Sulfur-containing medium | DMDS | DMDS | DMDS | DMDS |
| Hydrogen sulfide content in first paragraph circulation gas, μ L/L | 1000 | 1000 | 1000 | 1000 |
| Second segment reaction zone processing condition | ||||
| Catalyzer | Cracking catalyst | Cracking catalyst | Cracking catalyst | Cracking catalyst |
| 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 |
| Volume space velocity, h -1 | 3.0 | 3.0 | 3.0 | 3.0 |
| Average reaction temperature, DEG C | 290 | 290 | 290 | 290 |
| Runtime, h | 1000 | 100 | 300 | 700 |
| Pressure Drop, MPa | 0 | 0.1 | 0.3 | 0.7 |
| Spirit fraction | ||||
| Yield, quality % | 85 | 85 | 52 | 30 |
| Aromaticity content | Do not detect | Do not detect | Do not detect | Do not detect |
| Sulphur content, μ g/g | Do not detect | Do not detect | Do not detect | Do not detect |
| Boiling range scope, DEG C | 61～170 | 61～170 | 61～170 | 61～170 |
Yield with second segment reaction zone feeds for benchmark.
As can be seen from embodiment, bio-oil can direct production various high-quality low aromatic solvent oil production by the method for hydrotreating of this technology, by selecting different bio-oils, can production high-quality low aromatic solvent naphtha, and running is stable.
Claims (12)
1. produce a two-stage method method of hydrotreating for solvent oil, 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 the W of sulphided state, Mo, in Ni and Co one or more, in the beds that first reaction mass passes through, hydrogenation active component with the weight content of oxide basis for 3% ~ 10%, the hydrogenation active component content of the downstream catalyst that reaction mass passes through increases by 3 ~ 25 percentage points in oxide weight than adjacent upstream catalyzer,
C () first paragraph reaction zone hydrogenation effluent is separated into gas phase and liquid phase, recycle after gas-phase dehydration process at first paragraph,
Liquid phase enters the second segment reaction zone using hydrocracking catalyst after mixing with second segment reaction zone circulation gas, in response behaviour
Under, the active metal component of hydrocracking catalyst is one or more in W, Mo, Ni and Co of reduction-state;
D gas phase that () second segment reaction zone generates logistics recycles in second segment reaction zone, and second segment reaction zone generates logistics
Liquid phase fractionation in separation column obtain spirit fraction;
E () supplements S-contained substance in first paragraph reaction mass, to maintain hydrogen sulfide content in the circulation gas of first paragraph reaction zone.
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 of first paragraph reaction zone
Power 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.
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 bed 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 content of the downstream catalyst that reaction mass passes through increases by 5 ~ 20 percentage points in oxide weight 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
For 3.0MPa ~ 20.0MPa, 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℃~465℃。
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 hydrocracking catalyst of second segment reaction zone has cracking function, and hydrocracking catalyst contains Y type molecular sieve and/or ZSM-5 molecular sieve component; The hydrogenation active metals component of hydrocracking catalyst is with the weight content of oxide basis for 5% ~ 40%, and the weight content of molecular sieve component in hydrocracking catalyst is 5% ~ 60%.
10. in accordance with the method for claim 1, it is characterized in that: the sulfur-containing medium supplemented in the reaction mass of first paragraph reaction zone is the compound of sulfur-bearing.
11. in accordance with the method for claim 1, it is characterized in that: the sulfur-containing medium supplemented in the reaction mass of first paragraph reaction zone is the oil light-end products of sulfur-bearing.
12., according to the method described in claim 1 or 10, is characterized in that: in the circulation gas of first paragraph reaction zone, hydrogen sulfide content is not less than 0.005v%.
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| CN101089135A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Diesel oil fraction upgrading and pour point reducing 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 |
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| CN101089135A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Diesel oil fraction upgrading and pour point reducing 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 |
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