CN108728154A - A kind of production method of biomass base oil - Google Patents
A kind of production method of biomass base oil Download PDFInfo
- Publication number
- CN108728154A CN108728154A CN201810517743.4A CN201810517743A CN108728154A CN 108728154 A CN108728154 A CN 108728154A CN 201810517743 A CN201810517743 A CN 201810517743A CN 108728154 A CN108728154 A CN 108728154A
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- China
- Prior art keywords
- hydrogen
- base oil
- production method
- deoxidation
- biomass base
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
- C10G2300/1014—Biomass of vegetal origin
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
The present invention relates to field of renewable energy, specifically disclose a kind of production method of biomass base oil.The method comprises the following steps：(1) waste grease under hydroprocessing conditions in the presence of hydrogen, contacted with hydrotreating catalyst carry out plus hydrogen saturation, hydrogenation deoxidation, plus hydrogen decarbonylation base and plus hydrogen decarboxylation deoxidation saturated oils is obtained by the reaction；(2) deoxidation saturated oils in presence of hydrogen, two sections of hydro-isomerization pour point depressions of progress is contacted with heterogeneous catalyst and handle to obtain biomass base oil；Hydroprocessing condition is in step (1)：Hydrogen partial pressure 2.0~22.0MPa of power, hydrogen to oil volume ratio 100:1~3000:1, mass space velocity is 0.5h when liquid‑1~18h‑1, reaction temperature is 200~480 DEG C.This method can greatly improve the yield of the intermediate product deoxidation saturated oils of biomass base oil, and wherein the yield of deoxidation saturated oils is up to 95% or more.
Description
Technical field
The present invention relates to field of renewable energy, and in particular to a kind of production method of biomass base oil.
Background technology
Global economic expansion is pushing rapidly the demand to the energy, petroleum resources increasingly depleted to be generated using process dirty
Dye --- worldwide, the cry Continued of demand and reduction greenhouse gas emission for fuel, lubricating oil etc..It is useless
Grease is abandoned as renewable resource, its comprehensive utilization obtains worldwide extensive attention.
Waste grease obtains deoxidation saturated oils by hydrotreating, and deoxidation saturated oils exists with hydrogen under isomerization conditions
Under, the selective hydro-isomerization pour point depression of progress is contacted with heterogeneous catalyst, obtains biomass base oil, the biomass base oil
It is further useful for production gasoline, kerosene, diesel oil, lubricating oil, biowax etc..But the prior art adds hydrogen endless in process of production
Entirely, cause the yield of deoxidation saturated oils low, to further influence the performance of subsequent product.Therefore, biomass basis is being prepared
The yield of deoxidation saturated oils how is improved during oil becomes one of the technical issues of this field is badly in need of solving.
In addition, the prior art is during producing biomass base oil, on the one hand, in the hydrogen-rich gas after hydrogenation reaction
Containing a large amount of sulphur, COx, water, lower carbon number hydrocarbons etc., isomerization in bed carbon distribution and two sections of hydro-isomerization pour point depression processing procedures can be caused
The inactivation of catalyst, more catalyst changeout need to often be stopped work and can not directly return by causing shorten operation cycle, even if hydrogen can recycle,
But recycling high energy consumption；On the other hand, hydrogenation reaction stage and two sections of hydro-isomerization pour point depression processing are required to addition hydrogen
Gas, and expensive components of the hydrogen as raw material, therefore cause production cost that can not reduce.Therefore, how to reduce hydrogen dosage,
Hydrogen recycles energy consumption and ensures that catalyst activity stability is good and device long-period stable operation becomes this field and further needs
Technical problems to be solved.
Invention content
Primary technical problem to be solved by this invention is to provide a kind of production method of biomass base oil.This method
The yield of deoxidation saturated oils can be effectively improved.
Above-mentioned technical problem to be solved by this invention is achieved by the following technical programs：
A kind of production method of biomass base oil, comprises the following steps：(1) waste grease under hydroprocessing conditions and
In the presence of hydrogen, is contacted with hydrotreating catalyst and add hydrogen saturation, hydrogenation deoxidation plus hydrogen decarbonylation base and plus hydrogen decarboxylation
Deoxidation saturated oils is obtained by the reaction；(2) deoxidation saturated oils in presence of hydrogen, contacts with heterogeneous catalyst and carries out two sections of hydro-isomerizations
Pour point depression handles to obtain biomass base oil；
Hydroprocessing condition is in step (1)：Hydrogen partial pressure 2.0~22.0MPa of power, hydrogen to oil volume ratio 100:1~3000:1,
Mass space velocity is 0.5h when liquid-1~18h-1, reaction temperature is 200~480 DEG C.
It is further preferred that hydroprocessing condition is in step (1)：Hydrogen partial pressure 3.0~20.0MPa of power, hydrogen to oil volume ratio
200:1~2500:1, mass space velocity is 3h when liquid-1~12h-1, reaction temperature is 220~460 DEG C.
Preferably, the hydrotreating catalyst used in step (1) is loaded catalyst, wherein including following quality hundred
Divide the active constituent of ratio：28.0~40.0wt%WO3, 4.0~10.0wt%NiO, 1.8~5.0wt%MoO3。
Preferably, protective agent is also used in step (1) hydrogenation process；The protective agent is supported catalyst
Agent, wherein including the active constituent of following mass percent：1.0~4.0wt%NiO, 5.5~10.0wt%MoO3。
It is further preferred that the carrier of catalyst for hydrogenation is activated alumina, specific surface area is 200~400m2/
0.2~0.4mL/g of g, Kong Rongwei, can several apertures be 7~15nm.
It is further preferred that protectant carrier is activated alumina, specific surface area >=180m2/g, Kong Rong >=
0.60mL/g。
It is further preferred that the shape of catalyst for hydrogenation is butterfly.
It is further preferred that protectant shape is cloverleaf pattern.
Hydroprocessing condition controls and its intermediate product of the catalyst group that uses in the process biomass-based plinth oil in pairs takes off
Oxygen saturation oil yield influences very big；The state modulator of hydroprocessing condition is bad and hydrotreating and hydroprocessing processes
In catalyst choice do not have a greatly reduced quality to the yield that can make deoxidation saturated oils.The present invention gropes through a large amount of experiment, using this
Inventive method can greatly improve the yield of the intermediate product deoxidation saturated oils of biomass base oil.
Preferably, in entire reaction process, the Adding Way of hydrogen is：It is added in two sections of hydro-isomerization pour point depression processing stages
New hydrogen, the hydrogen-rich gas obtained after the processing of two sections of hydro-isomerization pour point depressions are recycled to the hydrogenation reaction stage, after the hydrogenation reaction stage
Obtained hydrogen-rich gas enters two sections of hydro-isomerization pour point depression processing stages together after de- impurity treatment with new hydrogen.
It is further preferred that the hydrogen-rich gas obtained after the hydrogenation reaction stage is through taking off the removing impurities matter described in impurity treatment
Refer to one or more kinds of mixing in desulfurization, decarburization oxide, dehydration and de- lower carbon number hydrocarbons C1~C4.
New hydrogen, two sections of hydro-isomerization drops are added in two sections of hydro-isomerization pour point depression processing stages in the selection that the present invention also innovates
The hydrogen-rich gas obtained after solidifying processing direct cycles to hydrogenation reaction stage, the hydrogen-rich obtained after the hydrogenation reaction stage without processing
Gas is connected to new hydrogen after de- impurity treatment and inputs two sections of hydro-isomerization pour point depression processing stages together.The benefit so recycled exists
In by the hydrogen circulation path of the innovation, may be implemented only to need to supplement new hydrogen in hydro-isomerization pour point depression, and only need to be
Hydrogenation reaction need to carry out recovery processing removal of impurities to hydrogen-rich gas, you can ensure that catalyst activity stability is good and device long period is steady
Fixed operation overcomes device in the prior art and shortens operation cycle, need to often stop work more catalyst changeout the problem of；Simultaneously so that hydrogen
Gas dosage and hydrogen recycling energy consumption substantially reduce, and reduce the production cost of oil hydrogenation technique.
Advantageous effect：(1) the present invention provides a kind of completely new biomass base oil, this method can greatly improve biomass
The yield of the intermediate product deoxidation saturated oils of base oil, wherein the yield of deoxidation saturated oils is up to 95% or more；(2) present invention wound
New prepares biodiesel using hydrogen adverse current oil hydrogenation method, by the hydrogen circulation path of the innovation, may be implemented only to need
New hydrogen is supplemented in hydro-isomerization pour point depression, and only recovery processing need to need to be carried out to hydrogen-rich gas in the hydrogenation reaction stage and removed
It is miscellaneous, you can ensure that catalyst activity stability is good and device long-period stable operation, overcome device in the prior art operate it is all
Phase shorten, need to often stop work more catalyst changeout the problem of；Simultaneously so that hydrogen usage and hydrogen recycling energy consumption substantially reduce, reduce
The production cost of oil hydrogenation technique.
Description of the drawings
Fig. 1 is the production method flow chart of biomass base oil of the present invention.
Specific implementation mode
The present invention is explained further below in conjunction with specific embodiment, but embodiment does not do any type of limit to the present invention
It is fixed.
Embodiment 1
A kind of production method of biomass base oil, it includes following steps：(1) hydrotreating is added in waste vegetable oil
In reactor, in presence of hydrogen, contacted with hydrotreating catalyst carry out plus hydrogen saturation, hydrogenation deoxidation, add hydrogen decarbonylation base with
And add hydrogen decarboxylation that deoxidation saturated oils is obtained by the reaction；(2) deoxidation saturated oils in presence of hydrogen, progress is contacted with heterogeneous catalyst
Two sections of hydro-isomerization pour point depressions handle to obtain biomass base oil；
In entire reaction process, the Adding Way of hydrogen is：New hydrogen is added in two sections of hydro-isomerization pour point depression processing stages,
The hydrogen-rich gas obtained after two sections of hydro-isomerization pour point depression processing is recycled to hydrogenation reaction stage, the richness obtained after the hydrogenation reaction stage
Hydrogen enters two sections of hydro-isomerization pour point depression processing stages together after amine washing method carries out de- impurity treatment with new hydrogen；It is described
Removing impurities matter refer to include desulfurization, decarburization oxide, dehydration and de- lower carbon number hydrocarbons C1~C4.
Hydroprocessing condition is in step (1)：Hydrogen partial pressure power 22.0MPa, hydrogen to oil volume ratio 3000:1, mass space velocity when liquid
For 18h-1, reaction temperature is 480 DEG C；The hydrotreating catalyst used in step (1) is loaded catalyst, wherein comprising such as
The active constituent of lower mass percent：31.9wt%WO3, 8.8wt%NiO, 3.2wt%MoO3；The carrier of catalyst is active oxygen
Change aluminium, specific surface area 325m2/ g, Kong Rongwei 0.36mL/g, can several apertures be 11.7nm, shape be butterfly；In addition, anti-
Should protective agent be also used in the process；The protective agent is loaded catalyst, wherein including the work of following mass percent
Property ingredient：3.1wt%NiO, 6.1wt%MoO3, protectant carrier is activated alumina, specific surface area 210m2/ g,
Hole holds 0.93mL/g, and shape is cloverleaf pattern.
The yield of the intermediate product deoxidation saturated oils for the biomass base oil being prepared after testing by this method is 96%.
Embodiment 2
A kind of production method of biomass base oil, it includes following steps：(1) hydrotreating reaction is added in hogwash fat
In device, in presence of hydrogen, is contacted with hydrotreating catalyst and add hydrogen saturation, hydrogenation deoxidation plus hydrogen decarbonylation base and add
Deoxidation saturated oils is obtained by the reaction in hydrogen decarboxylation；(2) deoxidation saturated oils in presence of hydrogen, two sections of progress is contacted with heterogeneous catalyst
Hydro-isomerization pour point depression handles to obtain biomass base oil；
In entire reaction process, the Adding Way of hydrogen is：New hydrogen is added in two sections of hydro-isomerization pour point depression processing stages,
The hydrogen-rich gas obtained after two sections of hydro-isomerization pour point depression processing is recycled to hydrogenation reaction stage, the richness obtained after the hydrogenation reaction stage
Hydrogen enters two sections of hydro-isomerization pour point depression processing stages together after amine washing method carries out de- impurity treatment with new hydrogen；It is described
Removing impurities matter refer to include desulfurization, decarburization oxide, dehydration and de- lower carbon number hydrocarbons C1~C4.
Hydroprocessing condition is in step (1)：Hydrogen partial pressure power 2.0MPa, hydrogen to oil volume ratio 200:1, mass space velocity is when liquid
0.5h-1, reaction temperature is 280 DEG C；The hydrotreating catalyst used in step (1) is loaded catalyst, wherein comprising such as
The active constituent of lower mass percent：36.5wt%WO3, 5.7wt%NiO, 2.1wt%MoO3；The carrier of catalyst is active oxygen
Change aluminium, specific surface area 221m2/ g, Kong Rongwei 0.23mL/g, can several apertures be 7.3nm, shape be butterfly；In addition, anti-
Should protective agent be also used in the process；The protective agent is loaded catalyst, wherein including the work of following mass percent
Property ingredient：2.5wt%NiO, 7.8wt%MoO3, protectant carrier is activated alumina, specific surface area 190m2/ g,
Hole holds 0.79mL/g, and shape is cloverleaf pattern.
The yield of the intermediate product deoxidation saturated oils for the biomass base oil being prepared after testing by this method is 98%.
1 bio-oil hydrogenation deoxidation of table is saturated oil ingredient distribution
2 bio-oil hydrogenation deoxidation saturated oils constitutive property of table
3 bio-oil hydrogenation deoxidation of table is saturated oil ingredient composition
Claims (10)
1. a kind of production method of biomass base oil, which is characterized in that comprise the following steps：(1) waste grease is adding at hydrogen
Under the conditions of reason and hydrogen in the presence of, contact with hydrotreating catalyst carry out plus hydrogen saturation, hydrogenation deoxidation, add hydrogen decarbonylation base and
Add hydrogen decarboxylation that deoxidation saturated oils is obtained by the reaction；(2) deoxidation saturated oils in presence of hydrogen, progress two is contacted with heterogeneous catalyst
Section hydro-isomerization pour point depression handles to obtain biomass base oil；
Hydroprocessing condition is in step (1)：Hydrogen partial pressure 2.0~22.0MPa of power, hydrogen to oil volume ratio 100:1~3000:1, when liquid
Mass space velocity is 0.5h-1~18h-1, reaction temperature is 200~480 DEG C.
2. the production method of biomass base oil according to claim 1, which is characterized in that hydrotreating in step (1)
Condition is：Hydrogen partial pressure 3.0~20.0MPa of power, hydrogen to oil volume ratio 200:1~2500:1, mass space velocity is 3h when liquid-1~12h-1,
Reaction temperature is 220~460 DEG C.
3. the production method of biomass base oil according to claim 1, which is characterized in that is used in step (1) adds
It is loaded catalyst that hydrogen, which handles catalyst, wherein including the active constituent of following mass percent：28.0~40.0wt%
WO3, 4.0~10.0wt%NiO, 1.8~5.0wt%MoO3。
4. the production method of biomass base oil according to claim 1, which is characterized in that step (1) hydrogenation reaction mistake
Protective agent is also used in journey；The protective agent be loaded catalyst, wherein comprising following mass percent activity at
Point：1.0~4.0wt%NiO, 5.5~10.0wt%MoO3。
5. the production method of biomass base oil according to claim 3, which is characterized in that the load of catalyst for hydrogenation
Body is activated alumina, and specific surface area is 200~400m20.2~0.4mL/g of/g, Kong Rongwei, can several apertures be 7~15nm.
6. the production method of biomass base oil according to claim 4, which is characterized in that protectant carrier is activity
Aluminium oxide, specific surface area >=180m2/g, Kong Rong >=0.60mL/g.
7. the production method of biomass base oil according to claim 3, which is characterized in that the shape of catalyst for hydrogenation
Shape is butterfly.
8. the production method of biomass base oil according to claim 4, which is characterized in that protectant shape
For cloverleaf pattern.
9. the production method of biomass base oil according to claim 1, which is characterized in that in entire reaction process, hydrogen
The Adding Way of gas is：New hydrogen is added in two sections of hydro-isomerization pour point depression processing stages, after two sections of hydro-isomerization pour point depression processing
To hydrogen-rich gas be recycled to the hydrogenation reaction stage, the hydrogen-rich gas obtained after the hydrogenation reaction stage is after de- impurity treatment with new
Hydrogen enters two sections of hydro-isomerization pour point depression processing stages together.
10. the production method of biomass base oil according to claim 9, which is characterized in that after the hydrogenation reaction stage
To hydrogen-rich gas through take off impurity treatment described in removing impurities matter refer to desulfurization, decarburization oxide, dehydration and de- lower carbon number hydrocarbons C1
One or more kinds of mixing in~C4.
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| CN201810517743.4A CN108728154A (en) | 2018-05-25 | 2018-05-25 | A kind of production method of biomass base oil |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105419867A (en) * | 2015-12-30 | 2016-03-23 | 胡平 | Combined hydrogenation method and apparatus utilizing biomass oil to produce green and environment-friendly transportation fuel |
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- 2018-05-25 CN CN201810517743.4A patent/CN108728154A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105419867A (en) * | 2015-12-30 | 2016-03-23 | 胡平 | Combined hydrogenation method and apparatus utilizing biomass oil to produce green and environment-friendly transportation fuel |
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Application publication date: 20181102 |