CN113174291B - Adsorption desulfurization method for biodiesel - Google Patents

Adsorption desulfurization method for biodiesel Download PDF

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CN113174291B
CN113174291B CN202110360470.9A CN202110360470A CN113174291B CN 113174291 B CN113174291 B CN 113174291B CN 202110360470 A CN202110360470 A CN 202110360470A CN 113174291 B CN113174291 B CN 113174291B
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biodiesel
adsorption
adsorbent
sulfur content
mesoporous
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CN113174291A (en
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于淑婷
韩立峰
张伟
李明时
鲁墨弘
张卫红
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Changzhou University
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11BPRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00Refining fats or fatty oils
    • C11B3/10Refining fats or fatty oils by adsorption
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/02Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C10L2290/542Adsorption of impurities during preparation or upgrading of a fuel
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels, e.g. bio-diesel

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Microbiology (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a biodiesel adsorption desulfurization method, which comprises the steps of adding an adsorbent and biodiesel to be desulfurized into a stirring reaction kettle, wherein the sulfur content in the biodiesel is 20-50mg/kg, the adsorption temperature is controlled to be between room temperature and 180 ℃, the adsorption pressure is controlled to be between normal pressure and 2.0MPa, and the adsorption time is controlled to be between 0.5 and 6 hours; the adsorbent is mesoporous carbon and/or Kong Mian resin, the mass ratio of the adsorbent to the biodiesel is 0.01-0.2, the pore volume of the mesoporous carbon is 1.5-2.5mL/g, the specific surface area is 1000-2000m 2/g, and the pore diameter is 3-10nm; the mesoporous melamine resin has a pore volume of 2.8-3.6mL/g, a specific surface area of 800-1200m 2/g and a pore diameter of 10-20nm. The biodiesel with the sulfur content of 20-50mg/kg can be reduced to less than 10mg/kg through adsorption, the process is simple, the cost is low, the condition is mild, and the environment is protected.

Description

Adsorption desulfurization method for biodiesel
Technical Field
The invention belongs to the technical field of adsorption desulfurization, and particularly relates to a biodiesel adsorption desulfurization method.
Background
With the increasingly strict requirements of environmental protection on the quality of diesel, the restrictions of the sulfur content of the diesel in various countries in the world are continuously improved. The national V standard, practiced since 2017, 1, requires that the sulfur content in diesel be no greater than 10mg/kg. In order to meet the national V standard, the development of the deep desulfurization technology of diesel oil has important significance. The desulfurization technology of diesel oil mainly comprises hydrodesulfurization and adsorption desulfurization. Compared with hydrodesulfurization, adsorption desulfurization has the characteristics of low equipment investment and mild operation conditions. The diesel adsorption desulfurizing agent reported in the current research mainly comprises an oxide adsorbent (such as SiO 2、-Al2O3, znO and the like), an oxide adsorbent for loading metals (Ni, K, ca) and a molecular sieve (A, X, MCM-41 and the like) adsorbent, and also comprises an adsorbent for loading CuCl by taking mesoporous carbon sheets as carriers.
The biodiesel is used as an environment-friendly renewable energy source and can be used as a supplement of fossil energy sources. Biodiesel has a chemical composition of fatty acid methyl or ethyl ester, and is usually prepared by transesterification of animal and vegetable oils (fatty acid triglycerides) with methanol or ethanol. The fatty acid triglyceride itself does not contain sulfur, so the biodiesel prepared by taking pure animal and vegetable oil as raw material does not need desulfurization. However, the biodiesel prepared from the waste animal and vegetable oil (commonly called swill-cooked dirty oil) is incapable of meeting the requirements of national V standard on the sulfur content of fuel oil because the residual food in the waste oil is decomposed during transportation and treatment, so that sulfur-containing compounds enter the waste oil. Sulfur in biodiesel is derived from decomposition of sulfur-containing compounds in residual food in swill-cooked dirty oil, the sulfur-containing compounds in biodiesel are mainly thioglucoside, isothiocyanate and oxazolidinethione, and belong to oxygen-containing and nitrogen-containing organic sulfides, and the sulfur content is usually only tens to hundreds of mg/kg. The sulfide in the conventional fossil diesel oil is mainly thiophene and derivatives thereof, the structure of the sulfide does not contain hetero atoms such as oxygen, nitrogen and the like, and the sulfur content is high, so that the sulfide is mostly thousands of mg/kg. Because the structure of the sulfur-containing compound in the biodiesel is different from that of the sulfur-containing compound in the fossil diesel, the adsorbent developed by the prior art aiming at the conventional fossil diesel adsorption desulfurization is not suitable for the adsorption desulfurization of the biodiesel, and the adsorption desulfurization technology aiming at the biodiesel needs to be developed.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a biodiesel adsorption desulfurization method.
In order to achieve the purpose of the invention, the technical scheme adopted is as follows: the adsorption desulfurizing process of biodiesel oil includes adding adsorbent and to-be-desulfurized biodiesel oil in stirring reactor with sulfur content of 20-50 mg/kg, controlled adsorption temperature of room temperature-180 deg.c, adsorption pressure of normal pressure-2.0 MPa and adsorption time of 0.5-6 hr; the adsorbent is mesoporous carbon and/or Kong Mian resin, the mass ratio of the adsorbent to biodiesel is 0.01-0.2, the pore volume of the mesoporous carbon is 1.5-2.5mL/g, the specific surface area is 1000-2000m 2/g, and the pore diameter is 3-10nm; the mesoporous melamine resin has a pore volume of 2.8-3.6mL/g, a specific surface area of 800-1200m 2/g and a pore diameter of 10-20nm.
Furthermore, the adsorbent is mesoporous carbon and mesoporous Kong Mian resin, the mass ratio of the mesoporous carbon to the mesoporous melamine resin is 4:6-6:4, and the mesoporous carbon and the mesoporous melamine resin are used together to have obvious synergistic effect, so that a better adsorption effect can be realized under the condition of a small amount of adsorbent.
Further, the mass ratio of the adsorbent to the biodiesel is 0.05-0.1, and the residence time is 1-3h.
Further, the adsorption temperature is 100-160 ℃.
Compared with the prior art, the invention has the following beneficial effects: the adsorption desulfurization method for biodiesel has obvious selective adsorption removal performance for trace sulfur-containing compounds in biodiesel produced by taking waste animal and vegetable oil as raw materials, and can reduce the sulfur content of biodiesel to less than 10mg/kg after adsorption, thereby meeting the national V standard requirement of diesel. The biodiesel adsorption desulfurization process has the advantages of simple flow, low equipment investment, mild operation conditions and environmental protection.
Detailed Description
The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in various other embodiments according to the present invention, or simply change or modify the design structure and thought of the present invention, which fall within the protection scope of the present invention. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention will be further described with reference to the following specific embodiments, but the scope of the invention is not limited thereto.
Example 1: 50g of biodiesel with 25mg/kg sulfur content is added into a 100mL round bottom flask, then 1g of medium Kong Mian resin adsorbent (with 3.6mL/g pore volume, 800m 2/g specific surface area and 20nm aperture) is added, the mixture is placed into a magnetic stirrer, nitrogen is filled to 2MPa, the temperature is raised to 180 ℃, stirring and adsorption are carried out for 4 hours at constant temperature, sampling is carried out, analysis is carried out by an ultraviolet fluorescence sulfur detector, and the sulfur content of the biodiesel after adsorption desulfurization is 9.4mg/kg.
Example 2: 50g of biodiesel with 25mg/kg sulfur content is added into a100 mL round bottom flask, then 2.5g of medium Kong Mian resin adsorbent (with 3.2mL/g pore volume, 1000m 2/g specific surface area and 15nm aperture) is added, the mixture is placed into a magnetic stirrer, nitrogen is filled to 1MPa, the temperature is raised to 160 ℃, stirring and adsorption are carried out at constant temperature for 3 hours, sampling is carried out, analysis is carried out by an ultraviolet fluorescence sulfur detector, and the sulfur content of the biodiesel after adsorption desulfurization is 8.5mg/kg.
Example 3: 50g of biodiesel with 25mg/kg sulfur content is added into a 100mL round bottom flask, 5g of medium Kong Mian resin adsorbent (with 2.8mL/g pore volume, 1200m 2/g specific surface area and 10nm aperture) is added, the mixture is placed into a magnetic stirrer, the temperature is raised to 120 ℃ under normal pressure, the mixture is stirred and adsorbed at constant temperature for 2 hours, then sampling is carried out, and the analysis is carried out by an ultraviolet fluorescence sulfur detector, wherein the sulfur content of the adsorbed and desulfurized biodiesel is 6.1mg/kg.
Example 4: 50g of biodiesel with the sulfur content of 50mg/kg is added into a 100mL round-bottom flask, 7.5g of medium Kong Mian resin adsorbent (with the pore volume of 3.2mL/g, the specific surface area of 1000m 2/g and the pore diameter of 15 nm) is added, the mixture is placed into a magnetic stirrer, the temperature is raised to 100 ℃ under normal pressure, the mixture is stirred and adsorbed at constant temperature for 5 hours, then sampling is carried out, and the analysis is carried out by an ultraviolet fluorescence sulfur detector, wherein the sulfur content of the adsorbed and desulfurized biodiesel is 8.7mg/kg.
Example 5: 50g of biodiesel with 25mg/kg sulfur content is added into a 100mL round bottom flask, 5g of mesoporous carbon adsorbent (with 2.5mL/g pore volume, 1000m 2/g specific surface area and 10nm aperture) is added, the mixture is placed into a magnetic stirrer, nitrogen is filled to 2MPa, the temperature is raised to 160 ℃, stirring and adsorption are carried out at constant temperature for 2h, sampling is carried out, analysis is carried out by an ultraviolet fluorescence sulfur detector, and the sulfur content of the biodiesel after adsorption desulfurization is 9.3mg/kg.
Example 6: 50g of biodiesel with 25mg/kg sulfur content is added into a 100mL round bottom flask, 7.5g of mesoporous carbon adsorbent (with 2.0mL/g pore volume, 1500m 2/g specific surface area and 6nm aperture) is added, the mixture is placed into a magnetic stirrer, the mixture is heated to 80 ℃ under normal pressure, stirred and adsorbed at constant temperature for 1h, then sampled, analyzed by an ultraviolet fluorescence sulfur analyzer, and the sulfur content of the adsorbed and desulfurized biodiesel is 8.3mg/kg.
Example 7: 50g of biodiesel with 25mg/kg sulfur content is added into a 100mL round bottom flask, 10g of mesoporous carbon adsorbent (with 1.5mL/g pore volume, 2000m 2/g specific surface area and 3nm aperture) is added, the mixture is placed into a magnetic stirrer, stirred and adsorbed for 2 hours at normal temperature and pressure, then sampled, analyzed by an ultraviolet fluorescence sulfur detector, and the sulfur content of the adsorbed and desulfurized biodiesel is 7.4mg/kg.
Example 8: 50g of biodiesel with 25mg/kg sulfur content is added into a 100mL round bottom flask, then 1.25g of mesoporous carbon (with the pore volume of 2.0mL/g, the specific surface area of 1500m 2/g and the pore diameter of 6 nm) and 1.25g of mesoporous Kong Mian resin (with the pore volume of 3.2mL/g, the specific surface area of 1000m 2/g and the pore diameter of 15 nm) are added into the flask, the mixture is fully ground and mixed to form an adsorbent, the adsorbent is placed into a magnetic stirrer, nitrogen is filled to 1MPa, the temperature is raised to 140 ℃, sampling is carried out after constant temperature stirring and adsorption for 2 hours, and the sulfur content of the biodiesel after adsorption desulfurization is 4.7mg/kg through analysis of an ultraviolet fluorescence sulfur analyzer.
Reference example 1: 50g of biodiesel with 25mg/kg sulfur content is added into a 100mL round bottom flask, 5g of ZnO adsorbent is added, the mixture is placed into a magnetic stirrer, the temperature is raised to 120 ℃ under normal pressure, the mixture is stirred and adsorbed for 3 hours at constant temperature, then the sample is taken, and the analysis is carried out by an ultraviolet fluorescence sulfur detector, wherein the sulfur content of the biodiesel after adsorption desulfurization is 17mg/kg.
Reference example 2: 50g of biodiesel with 25mg/kg sulfur content is added into a 100mL round-bottom flask, 5g of SiO 2 adsorbent is added, the mixture is placed into a magnetic stirrer, nitrogen is filled to 2MPa, the temperature is raised to 160 ℃, stirring and adsorption are carried out at constant temperature for 2h, and then sampling is carried out. Analyzed by an ultraviolet fluorescence sulfur detector, the sulfur content of the biodiesel after adsorption desulfurization is 18mg/kg.
Reference example 3: 50g of biodiesel with 25mg/kg sulfur content is added into a 100mL round-bottom flask, 5g of Al 2O3 adsorbent is added, the mixture is placed into a magnetic stirrer, the temperature is raised to 100 ℃ under normal pressure, and the mixture is stirred and adsorbed for 4 hours at constant temperature and then sampled. Analyzed by an ultraviolet fluorescence sulfur detector, the sulfur content of the biodiesel after adsorption desulfurization is 15mg/kg.
Reference example 4: 50g of biodiesel with 25mg/kg sulfur content is added into a 100mL round bottom flask, 5g of conventional melamine resin adsorbent (with 0.8mL/g pore volume, 400m 2/g specific surface area and 8nm aperture) is added, the mixture is placed into a magnetic stirrer, the temperature is raised to 120 ℃ under normal pressure, the mixture is stirred and adsorbed at constant temperature for 2 hours, then sampling is carried out, and the analysis is carried out by an ultraviolet fluorescence sulfur detector, wherein the sulfur content of the adsorbed and desulfurized biodiesel is 14mg/kg.
Reference example 5: 50g of biodiesel with 25mg/kg sulfur content is added into a 100mL round bottom flask, 5g of conventional mesoporous carbon adsorbent (with 0.8mL/g pore volume, 900m 2/g specific surface area and 4nm pore diameter) is added, the mixture is placed into a magnetic stirrer, nitrogen is filled to 2MPa, the temperature is raised to 160 ℃, stirring and adsorption are carried out at constant temperature for 2 hours, sampling is carried out, analysis is carried out by an ultraviolet fluorescence sulfur detector, and the sulfur content of the biodiesel after adsorption desulfurization is 19mg/kg.
The control of the pressure is mainly to prevent volatilization of the raw material at an elevated temperature, but the pressure has little influence on the adsorption effect of sulfur in biodiesel.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme and the concept of the present invention, and should be covered by the scope of the present invention.

Claims (4)

1. A biodiesel adsorption desulfurization method is characterized in that: adding an adsorbent and biodiesel to be desulfurized into a stirring reaction kettle, wherein the sulfur content in the biodiesel is 20-50 mg/kg, the adsorption temperature is controlled to be room temperature-180 ℃, the adsorption pressure is controlled to be normal pressure-2.0 MPa, and the adsorption time is controlled to be 0.5-6h; the adsorbent is medium Kong Mian resin or a mixture of mesoporous melamine resin and mesoporous carbon; the mass ratio of the adsorbent to the biodiesel is 0.01-0.2, the pore volume of the mesoporous carbon is 1.5-2.5mL/g, the specific surface area is 1000-2000m 2/g, and the pore diameter is 3-10nm; the mesoporous melamine resin has a pore volume of 2.8-3.6mL/g, a specific surface area of 800-1200m 2/g and a pore diameter of 10-20nm.
2. The method for adsorption desulfurization of biodiesel according to claim 1, characterized in that: the adsorbent is mesoporous carbon and mesoporous Kong Mian resin, and the mass ratio of the mesoporous carbon to the mesoporous melamine resin is 4:6-6:4.
3. The method for adsorption desulfurization of biodiesel according to claim 1, characterized in that: the mass ratio of the adsorbent to the biodiesel is 0.05-0.1, and the residence time is 1-3h.
4. The method for adsorption desulfurization of biodiesel according to claim 1, characterized in that: the adsorption temperature is 100-160 ℃.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101323794A (en) * 2008-07-28 2008-12-17 华东理工大学 Spherical active carbon fuel oil adsorption desulfurizing agent and preparation thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101323794A (en) * 2008-07-28 2008-12-17 华东理工大学 Spherical active carbon fuel oil adsorption desulfurizing agent and preparation thereof

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