CN103102918A - 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 take bio-oil as stock oil, the two-stage method method of hydrotreating of direct production solvent oil.
Background technology
The world economy sustainable development, at present in 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, except being improved, existing oil Refining Technologies seeks new oil substitutes, 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 chief component is carbon, hydrogen and oxygen, and very similar to the composition of alkane, alcohol, ether etc., 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 cuts 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 the low freezing point diesel fuel cut with animal-plant oil.
Comprise in the bio-oil hydrogenation process of aforesaid method, one of subject matter that runs into is that the bed carbon distribution causes shortening running period, the more catalyst changeout of need to often stopping work, and also 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.High-grade low aromatic solvent naphtha raw materials for production are limited at present (generally only limits to gasoline fraction or the kerosene(oil)fraction of paraffinic crude, perhaps 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, has limited the production of high-grade low aromatic solvent naphtha.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of two-stage method method of hydrotreating of producing solvent oil, separately take bio-oil as stock oil, first paragraph uses the sulphided state hydrogenation catalyst of grating, second segment uses the reduction-state hydrocracking catalyst, the characteristics such as direct production solvent oil under the condition of hydrogenation has hydrogenation process and stablizes, and running period is long.
A kind of two-stage method method of hydrotreating of producing solvent oil of the present invention comprises following content:
(a) one or more in bio-oil are stock oil;
(b) under the hydroprocessing condition, stock oil and hydrogen are by the first paragraph reaction zone, the first paragraph reaction zone comprises the hydrogenation catalyst bed that at least two hydrogenation activity component concentrations raise successively, stock oil and hydrogen are 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 one or more in W, Mo, Ni and the Co of sulphided state;
(c) first paragraph reaction zone hydrogenation effluent is separated into gas phase and liquid phase, gas-phase dehydration recycles at first paragraph after processing, liquid phase with enter the second segment reaction zone that uses hydrocracking catalyst after second segment reaction zone circulation gas mixes, under response behaviour, the active metal component of hydrocracking catalyst is one or more in W, Mo, Ni and the Co of reduction-state;
(d) gas phase of second segment reaction zone generation logistics recycles at the second segment reaction zone, and liquid phase fractionation in separation column that the second segment reaction zone generates logistics obtains the solvent oil cut;
(e) replenish S-contained substance in the first paragraph reaction mass, to keep hydrogen sulfide content in first paragraph reaction zone circulation gas.
In the inventive method step (a), the bio-oil that uses 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 condition 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, 180 ℃ ~ 465 ℃ of average reaction temperature; 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, 200 ℃ ~ 445 ℃ of average reaction temperature.
In the inventive method step (b), first paragraph reaction zone beds generally can arrange 2 ~ 5, in the beds that at first reaction mass passes through, the hydrogenation activity component is take the weight content of oxide compound as 3%～10%, the hydrogenation catalyst that at first reaction mass passes through accounts for 10% ~ 80% of all hydrogenation catalyst volumes of first paragraph reaction zone, preferred 20% ~ 70%, best 30% ~ 60%.The hydrogenation activity component concentration 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 simultaneously, as P, Si, B, Ti, Zr etc.Can adopt the commercial catalyst, also can be by the existing method preparation in this area.the business hydrogenation catalyst that the first paragraph reaction zone uses mainly contains, 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.First paragraph reaction zone hydrogenation effluent separates can comprise fractionating system, also can not comprise fractionating system (only comprising Separate System of Water-jet).When comprising fractionating system, the middle runnings (being diesel oil distillate) that the fractionating system fractionation is obtained enters the second segment reaction zone.
In the inventive method step (b), first paragraph reaction zone hydrogenation activity component is the catalyzer of oxidation state, carries out conventional sulfidizing before using, and makes the hydrogenation activity component be converted into sulphided state, perhaps uses the outer good catalyzer of prevulcanized of device.
In the inventive method step (c), the hydroprocessing condition 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, 180 ℃ ~ 465 ℃ of average reaction temperature; 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, 200 ℃ ~ 445 ℃ of average reaction temperature.First paragraph reaction zone hydrogenation effluent need not lowered the temperature and be carried 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 that enters the second segment reaction zone can be the liquid phase material after the gas-liquid separation of first paragraph reaction zone, can be also the liquid phase material intermediate oil that fractionation obtains through separation column after the gas-liquid separation of first paragraph reaction zone.
In the inventive method step (c), the hydrocracking catalyst of second segment reaction zone has the cracking function, as contains the components such as Y zeolite and/or ZSM-5 molecular sieve.The hydrogenation active metals component of hydrocracking catalyst is generally 5%～40% in the weight content of oxide compound.The weight content of molecular sieve component in hydrocracking catalyst is generally 5%～60%.Can contain simultaneously other refractory inorganic oxides in hydrocracking catalyst.The commercial catalysts that the second segment reaction zone uses mainly contains, 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 ℃～500 ℃ temperature before use, reduces under preferred 220 ℃～450 ℃ conditions.Whenever forbid to inject sulfur-bearing, nitrogenous medium in the second segment system, avoid poisoning of catalyst.
In the inventive method step (d), the low aromatic solvent naphtha that obtains is the mixed solvent oil distillate, can continue according to the actual requirements fractionation 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 naphtha.Specifically can specifically 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 that replenishes 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, and CS
2Deng, can be also the oil light-end products of sulfur-bearing, as the petroleum naphtha of sulfur-bearing, boat coal etc.By replenishing of sulphur, can guarantee that the hydrogen sulfide content in first paragraph reaction zone circulation gas is not less than 0.005v%, preferred 0.01v%～2.0v%.
In prior art bio-oil usually by separately or with the method for the method production automotive fuel of other petroleum products mixings back end hydrogenations.The present invention uses grating technology and the operational condition of reduction-state hydrogenation catalyst by optimization, first paragraph hydrotreatment (sulfurized hydrogenation catalyst of grating), second segment hydrocracking (reduced form hydrocracking catalyst) can be directly take bio-oil as the raw material production low aromatic solvent naphtha.The present invention has expanded the raw material sources of high added value low aromatic solvent naphtha, and production cost is low, can further improve added value of product.
Description of drawings
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: the mixing oil of one or more in the bio-oil is as stock oil, under the hydroprocessing condition, stock oil and hydrogen are by comprising the first paragraph hydroconversion reaction zone of at least two kinds of hydrogenation catalysts, the hydrogenated oil that obtains separates in high-pressure separator (abbreviation high score) gas that obtains and recycles at the first paragraph reaction zone, the liquid distillate that obtains and hydrogen are mixed into and comprise the second segment reaction zone with cracking performance Nobel metal hydrogen cracking catalyst, obtaining the hydrocracking logistics recycles at second segment at the gas that high-pressure separator (abbreviation high score) separation obtains, the liquid fractionation that obtains obtains all kinds of SOLVENTS oil production, also consider at first paragraph, a part of middle runnings and unconverted oil to be looped back the first paragraph reaction zone.The bio-oil that embodiment uses is the commercially available prod, filtering solid impurity before using.
Further illustrate particular case of the present invention below by embodiment.
The chief component of table 1 hydrogenation catalyst and character.
| Catalyzer | Catalyzer 1 | Catalyzer 2 | Catalyzer 3 | 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 |
| The 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 |
| The entrance hydrogen to oil volume ratio | 1500:1 | 1000:1 | 1000:1 |
| The cumulative volume air speed, h -1 | 1.0 | 1.5 | 0.4 |
| Average reaction temperature, ℃ | 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 |
| The 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, ℃ | 280 | 340 | 300 |
| The solvent oil cut | ? | ? | ? |
| 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 |
| The boiling range scope, ℃ | 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 |
| The 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 |
| 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, ℃ | 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 |
| The 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, ℃ | 290 | 290 | 290 | 290 |
| Runtime, h | 1000 | 100 | 300 | 700 |
| Pressure Drop, MPa | 0 | 0.1 | 0.3 | 0.7 |
| The solvent oil cut | ? | ? | ? | ? |
| 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 |
| The boiling range scope, ℃ | 61～170 | 61～170 | 61～170 | 61～170 |
Yield is take the second segment reaction zone feeds as benchmark.
Can be found out by embodiment, the method for hydrotreating of bio-oil by present technique can the various high-quality low aromatic solvent of direct production oil production, by selecting different bio-oils, can production high-quality low aromatic solvent naphtha, and running is stable.
Claims (10)
1. two-stage method method of hydrotreating of producing solvent oil is characterized in that comprising following content:
(a) one or more in bio-oil are stock oil;
(b) under the hydroprocessing condition, stock oil and hydrogen are by the first paragraph reaction zone, the first paragraph reaction zone comprises the hydrogenation catalyst bed that at least two hydrogenation activity component concentrations raise successively, stock oil and hydrogen are 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 one or more in W, Mo, Ni and the Co of sulphided state;
(c) first paragraph reaction zone hydrogenation effluent is separated into gas phase and liquid phase, gas-phase dehydration recycles at first paragraph after processing, liquid phase with enter the second segment reaction zone that uses hydrocracking catalyst after second segment reaction zone circulation gas mixes, under response behaviour, the active metal component of hydrocracking catalyst is one or more in W, Mo, Ni and the Co of reduction-state;
(d) gas phase of second segment reaction zone generation logistics recycles at the second segment reaction zone, and liquid phase fractionation in separation column that the second segment reaction zone generates logistics obtains the solvent oil cut;
(e) replenish S-contained substance in the first paragraph reaction mass, to keep hydrogen sulfide content in first paragraph reaction zone 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, 180 ℃ ~ 465 ℃ of average reaction temperature.
4. in accordance with the method for claim 1, it is characterized in that: in step (b), the reaction pressure 3.0MPa of first paragraph reaction zone ~ 18.0MPa, hydrogen to oil volume ratio 300:1 ~ 2500:1, volume space velocity 0.2h
-1~ 4.0h
-1, 200 ℃ ~ 445 ℃ of average reaction temperature.
5. according to the described method of claim 1 or 3, it is characterized in that: in step (b), first paragraph reaction zone beds arranges 2 ~ 5, in the beds that at first reaction mass passes through, the hydrogenation activity component is take the weight content of oxide compound as 3%～10%, and the hydrogenation catalyst bed that at first reaction mass passes through accounts for 10% ~ 80% of all hydrogenation catalyst volumes of first paragraph reaction zone; The hydrogenation activity component concentration of the downstream catalyst that reaction mass passes through increases by 3～25 percentage points in oxide weight than adjacent upstream catalyzer.
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 at first reaction mass passes through accounts for 20% ~ 70% of all hydrogenation catalyst volumes of first paragraph reaction zone, and the hydrogenation activity component concentration 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 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, 180 ℃ ~ 465 ℃ of average reaction temperature, preferred reaction pressure is that 3.0MPa ~ 18.0MPa hydrogen to oil volume ratio is 300:1 ~ 2500:1, volume space velocity is 0.4h
-1~ 4.0h
-1, average reaction temperature is 200 ℃ ~ 445 ℃.
8. 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 the cracking function, and hydrocracking catalyst contains Y zeolite and/or ZSM-5 molecular sieve component; The hydrogenation active metals component of hydrocracking catalyst is take the weight content of oxide compound as 5%～40%, and the weight content of molecular sieve component in hydrocracking catalyst is 5%～60%.
9. in accordance with the method for claim 1, it is characterized in that: the sulfur-containing medium that replenishes in first paragraph reaction zone reaction mass is the compound of sulfur-bearing, or the oil light-end products of sulfur-bearing.
10. according to the described method of claim 1 or 9, it is characterized in that: in first paragraph reaction zone circulation gas, hydrogen sulfide content is not less than 0.005v%.
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| CN106622267A (en) * | 2015-11-02 | 2017-05-10 | 中国石油化工股份有限公司 | Residual oil hydrotreating catalyst and preparation method thereof |
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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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| CN106622267A (en) * | 2015-11-02 | 2017-05-10 | 中国石油化工股份有限公司 | Residual oil hydrotreating catalyst and preparation method thereof |
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