CN114196481A - Preparation method of cottonseed oil and saponin biological oleic acid - Google Patents

Preparation method of cottonseed oil and saponin biological oleic acid Download PDF

Info

Publication number
CN114196481A
CN114196481A CN202111408744.3A CN202111408744A CN114196481A CN 114196481 A CN114196481 A CN 114196481A CN 202111408744 A CN202111408744 A CN 202111408744A CN 114196481 A CN114196481 A CN 114196481A
Authority
CN
China
Prior art keywords
cottonseed oil
saponin
oil
oleic acid
reactor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202111408744.3A
Other languages
Chinese (zh)
Inventor
买买提·玉努斯
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Aksu Harluk Biotechnology Co ltd
Original Assignee
Xinjiang Huaxiong Renewable Resources Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xinjiang Huaxiong Renewable Resources Technology Co ltd filed Critical Xinjiang Huaxiong Renewable Resources Technology Co ltd
Priority to CN202111408744.3A priority Critical patent/CN114196481A/en
Publication of CN114196481A publication Critical patent/CN114196481A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, 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
    • C11B13/00—Recovery of fats, fatty oils or fatty acids from waste materials
    • C11B13/02—Recovery of fats, fatty oils or fatty acids from waste materials from soap stock
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/10—Vacuum distillation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B01J19/0013—Controlling the temperature of the process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/1802—Organic compounds containing oxygen natural products, e.g. waxes, extracts, fatty oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/12—Use of additives to fuels or fires for particular purposes for improving the cetane number
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00054—Controlling or regulating the heat exchange system
    • B01J2219/00056—Controlling or regulating the heat exchange system involving measured parameters
    • B01J2219/00058—Temperature measurement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00162—Controlling or regulating processes controlling the pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00164—Controlling or regulating processes controlling the flow
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00184—Controlling or regulating processes controlling the weight of reactants in the reactor vessel
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/74—Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to the technical field of biodiesel preparation, in particular to a method for preparing cottonseed oil saponin biological oleic acid, which comprises the steps of filling a solid acid catalyst in a reactor, adjusting the hydrogen pressure and flow of the reactor, slowly heating, introducing pre-vulcanized oil, and completing pre-vulcanization of the catalyst; pre-esterifying cottonseed oil saponin; introducing the pre-esterified cottonseed oil saponin and the straight-run diesel oil into a pre-vulcanized reactor, and carrying out hydrogenation mixing. Compared with the prior art, the method for preparing the biological oleic acid by using the cottonseed oil saponin provided by the invention has the advantages that the cottonseed oil saponin is subjected to pre-esterification, the pre-esterification rate reaches 95.93-96.11%, the acid value is reduced to 2.5-2.9KOH/g, then the pre-esterified cottonseed oil saponin is added into straight-run diesel oil for hydrogenation mixing, the cetane number of a product is obviously improved, the component yield of the diesel oil is improved, the density of a diesel oil fraction is reduced, and the hydrogen consumption is reduced.

Description

Preparation method of cottonseed oil and saponin biological oleic acid
Technical Field
The invention relates to the technical field of biodiesel preparation, and particularly relates to a preparation method of cottonseed oil and saponin biological oleic acid.
Background
Because of limited petroleum energy resources, with the rapid development of world industry, the energy consumption is rapidly increased, so that the petroleum price is continuously increased and the problem of energy safety faces the world. The petroleum energy is used and produced at the present speed, and the petroleum resources in the world are likely to be exhausted within 50 years. Meanwhile, with the increasing awareness of environmental protection of people in modern society, people gradually recognize how serious air pollution is caused by automobile exhaust emission. Therefore, the search for alternative fuels that are abundant in resources, environmentally friendly, and economically feasible has become a major problem to be solved by mankind. Among them, biodiesel is the most remarkable one. It can be used as chemical raw material and diesel fuel. Compared with the traditional diesel oil, the biodiesel has the advantages that the raw material can be regenerated, and the dependence on petroleum is reduced; the lubricating property is good; safe storage, transportation and use and good anti-knock property; biodegradable and is a renewable resource; is non-toxic and completely combusted, and is an environment-friendly fuel. At present, biodiesel is regarded by various countries as a substitute for petroleum diesel.
The production method of the biodiesel comprises a physical method: micro emulsified oil formed by mixing animal and vegetable oil and diesel oil. The biological method has the advantages of mild conditions, less energy consumption, less alcohol consumption and the like, but the lipase activity is easily inhibited and inactivated by low-carbon alcohol, and the method has the defects of slow reaction rate, high cost and the like, and has no industrial successful application example. Chemical processes include acid, alkaline and a combination of the two steps. The acid method can solve the problem that the raw material with high acid value is difficult to utilize, but the reaction process is long in time and the requirement on the corrosion resistance of equipment is high; the alkaline method has strict requirements on the grease raw materials, the reaction process is complex, and the subsequent treatment cost is high. Although the chemical method has been widely used in industry, there are problems that the catalyst is difficult to recover, the by-product glycerol is difficult to purify, a large amount of wastewater is generated in the subsequent treatment, and the like.
Disclosure of Invention
Aiming at the defects of the background technology, the invention provides a preparation method and application of cottonseed oil and saponin biological oleic acid.
The technical scheme adopted by the invention is as follows: the key point of the preparation method of the biological oleic acid with cottonseed oil and saponin is as follows: s1, filling a solid acid catalyst in the reactor, adjusting the hydrogen pressure and flow of the reactor, slowly heating to 110-120 ℃, dehydrating for 2h, introducing pre-vulcanized oil, and keeping the temperature constant for 6h after the temperature is programmed to 320 ℃ to finish the pre-vulcanization of the catalyst;
s2, pre-esterifying cottonseed oil saponin;
s3, cooling the pre-vulcanized reactor to 280 ℃, and introducing a mixture of the components in a mass ratio of 1: and (5-8) adjusting the hydrogen pressure and flow of the reactor until reaction conditions are reached, and reacting for 2-6h to obtain the finished product.
Preferably, the solid acid catalyst is CoMo/gamma-Al2O3。
Preferably, the temperature raising conditions in S1 are: keeping the temperature at 200 ℃ for 1h, keeping the temperature at 240 ℃ for 1h, keeping the temperature at 280 ℃ for 1h, and keeping the temperature at 300 ℃ for 1 h.
Preferably, the pressure of hydrogen in S1 is 3MPa, and the space velocity is 2h-1The hydrogen-oil ratio was 500.
Preferably, S2 is specifically: heating cottonseed oil to 80 ℃, adding methanol and a pre-ester catalyst, stirring vigorously, reacting for 1-2h under the condition of reflux, cooling and stopping the reaction, standing and layering reactants, taking an upper layer mixture, and distilling under reduced pressure to obtain the pre-esterified cottonseed oil.
Preferably, the pressure of hydrogen in S3 is 3Mpa, the temperature is 320 ℃, and the space velocity is 2h-1The hydrogen-oil ratio was 500.
Preferably, the pre-ester catalyst is prepared by the following method: 20ml of TiCl are added4Slowly adding into 400ml distilled water, dropwise adding 28% wt ammonia water under strong stirring until the pH of the solution is 9-10, standing and aging at-5 deg.C for 24h, filtering, and washing until no Cl is formed-Drying at 110 ℃ for 24h to obtain Ti (OH)4A mixture of Ti (OH)4Is placed at 0.5-1.5mol/L (NH4)2S2O8After being soaked for 4-6h, the mixture is dried and roasted at 425-575 ℃.
Has the advantages that: compared with the prior art, the method for preparing the biological oleic acid by using the cottonseed oil saponin provided by the invention has the advantages that the cottonseed oil saponin is subjected to pre-esterification, the pre-esterification rate reaches 95.93-96.11%, the acid value is reduced to 2.5-2.9KOH/g, then the pre-esterified cottonseed oil saponin is added into straight-run diesel oil for hydrogenation mixing, the cetane number of a product is obviously improved, the component yield of the diesel oil is improved, the density of a diesel oil fraction is reduced, and the hydrogen consumption is reduced.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the present invention will be described in detail with reference to the specific embodiments shown in the attached table.
Example 1 preparation method of biological oleic acid from cottonseed oil and saponin
S1, filling the reactor with CoMo/gamma-Al2O3Adjusting the hydrogen pressure and flow of the reactor, wherein the hydrogen pressure is 3Mpa, and the space velocity is 2h-1Slowly heating to 110 ℃ at a hydrogen-oil ratio of 500, dehydrating for 2h, introducing pre-vulcanized oil, keeping the temperature constant at 200 ℃ for 1h, keeping the temperature constant at 240 ℃ for 1h, keeping the temperature constant at 280 ℃ for 1h, keeping the temperature constant at 300 ℃ for 1h, heating to 320 ℃ and keeping the temperature constant for 6h to finish the pre-vulcanization of the catalyst;
s2, heating cottonseed oil to 80 ℃, adding methanol and a pre-esterification catalyst, stirring vigorously, reacting for 1-2h under a reflux condition, cooling and stopping the reaction, standing and layering reactants, taking an upper-layer mixture, and distilling under reduced pressure to obtain pre-esterified cottonseed oil; the pre-ester catalyst is prepared by the following method: 20ml of TiCl are added4Slowly adding into 400ml distilled water, dropwise adding 28% wt ammonia water under strong stirring until the pH of the solution is 9, standing and aging at-5 deg.C for 24 hr, filtering, and washing until no Cl is formed-Drying at 110 ℃ for 24h to obtain Ti (OH)4A mixture of Ti (OH)4Placed at 0.5mol/L (NH4)2S2O8After being soaked for 4-6h, the mixture is dried and roasted at 425-575 ℃;
s3, cooling the pre-vulcanized reactor to 280 ℃, and introducing a mixture of the components in a mass ratio of 1: 5, regulating the hydrogen pressure and flow of the reactor until the hydrogen pressure reaches the value of3Mpa, 320 ℃ and 2h of space velocity-1And reacting for 2 hours to obtain a finished product, wherein the hydrogen-oil ratio is 500.
And (4) detecting a result: the product oil had a cetane number of 58, viscosity (40 ℃) of 5.12, sulfur content of 333 mu g/g, and nitrogen content of 201 mu g/g.
Example 2 preparation method of biological oleic acid from cottonseed oil and saponin
S1, filling the reactor with CoMo/gamma-Al2O3Adjusting the hydrogen pressure and flow of the reactor, wherein the hydrogen pressure is 3Mpa, and the space velocity is 2h-1Slowly heating to 120 ℃ at a hydrogen-oil ratio of 500, dehydrating for 2h, introducing pre-vulcanized oil, keeping the temperature constant at 200 ℃ for 1h, keeping the temperature constant at 240 ℃ for 1h, keeping the temperature constant at 280 ℃ for 1h, keeping the temperature constant at 300 ℃ for 1h, heating to 320 ℃ and keeping the temperature constant for 6h to finish the pre-vulcanization of the catalyst;
s2, heating cottonseed oil to 80 ℃, adding methanol and a pre-esterification catalyst, stirring vigorously, reacting for 1-2h under a reflux condition, cooling and stopping the reaction, standing and layering reactants, taking an upper-layer mixture, and distilling under reduced pressure to obtain pre-esterified cottonseed oil; the pre-ester catalyst is prepared by the following method: 20ml of TiCl are added4Slowly adding into 400ml distilled water, dropwise adding 28% wt ammonia water under strong stirring until the pH of the solution is 10, standing and aging at-5 deg.C for 24h, filtering, and washing until no Cl is formed-Drying at 110 ℃ for 24h to obtain Ti (OH)4A mixture of Ti (OH)4Placed at 1.5mol/L (NH4)2S2O8After being soaked for 4-6h, the mixture is dried and roasted at 425-575 ℃;
s3, cooling the pre-vulcanized reactor to 280 ℃, and introducing a mixture of the components in a mass ratio of 1: 8, regulating the hydrogen pressure and flow of the reactor until the hydrogen pressure reaches 3Mpa, the temperature reaches 320 ℃, and the airspeed reaches 2h-1And reacting for 6 hours to obtain a finished product, wherein the hydrogen-oil ratio is 500.
And (4) detecting a result: the product oil had a cetane number of 50, viscosity (40 ℃) of 5.54, sulfur content of 332. mu.g/g, and nitrogen content of 208. mu.g/g.
Example 3 preparation method of biological oleic acid from cottonseed oil and saponin
S1, filling the reactor with CoMo/gamma-Al2O3Adjusting the hydrogen pressure and flow of the reactor, wherein the hydrogen pressure is 3Mpa, and the space velocity is 2h-1Slowly heating to 115 ℃ at a hydrogen-oil ratio of 500, dehydrating for 2h, introducing pre-vulcanized oil, keeping the temperature constant at 200 ℃ for 1h, keeping the temperature constant at 240 ℃ for 1h, keeping the temperature constant at 280 ℃ for 1h, keeping the temperature constant at 300 ℃ for 1h, heating to 320 ℃ and keeping the temperature constant for 6h to finish the pre-vulcanization of the catalyst;
s2, heating cottonseed oil to 80 ℃, adding methanol and a pre-esterification catalyst, stirring vigorously, reacting for 1-2h under a reflux condition, cooling and stopping the reaction, standing and layering reactants, taking an upper-layer mixture, and distilling under reduced pressure to obtain pre-esterified cottonseed oil; the pre-ester catalyst is prepared by the following method: 20ml of TiCl are added4Slowly adding into 400ml distilled water, dropwise adding 28% wt ammonia water under strong stirring until the pH of the solution is 9, standing and aging at-5 deg.C for 24 hr, filtering, and washing until no Cl is formed-Drying at 110 ℃ for 24h to obtain Ti (OH)4A mixture of Ti (OH)4Placed at 1.0mol/L (NH4)2S2O8After being soaked for 4-6h, the mixture is dried and roasted at 425-575 ℃;
s3, cooling the pre-vulcanized reactor to 280 ℃, and introducing a mixture of the components in a mass ratio of 1: 7, regulating the hydrogen pressure and flow of the reactor until the hydrogen pressure reaches 3Mpa, the temperature reaches 320 ℃, and the airspeed reaches 2h-1And reacting for 3 hours to obtain a finished product, wherein the hydrogen-oil ratio is 500.
And (4) detecting a result: the product oil had a cetane number of 53, viscosity (40 ℃) of 5.39, sulfur content of 357. mu.g/g, and nitrogen content of 216. mu.g/g.
It should be noted that the above-mentioned embodiments illustrate only preferred embodiments of the invention, and that those skilled in the art will be able to make many alternative embodiments without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (7)

1. The preparation method of the biological oleic acid with cottonseed oil and saponin is characterized by comprising the following steps:
s1, filling a solid acid catalyst in the reactor, adjusting the hydrogen pressure and flow of the reactor, slowly heating to 110-120 ℃, dehydrating for 2h, introducing pre-vulcanized oil, and keeping the temperature constant for 6h after the temperature is programmed to 320 ℃ to finish the pre-vulcanization of the catalyst;
s2, pre-esterifying cottonseed oil saponin;
s3, cooling the pre-vulcanized reactor to 280 ℃, and introducing a mixture of the components in a mass ratio of 1: and (5-8) adjusting the hydrogen pressure and flow of the reactor until reaction conditions are reached, and reacting for 2-6h to obtain the finished product.
2. The method for preparing biological oleic acid from cottonseed oil and saponin as claimed in claim 1, wherein: the solid acid catalyst is CoMo/gamma-Al2O3。
3. The method for preparing biological oleic acid from cottonseed oil saponin as claimed in claim 1, wherein the temperature rise conditions in the S1 program are as follows: keeping the temperature at 200 ℃ for 1h, keeping the temperature at 240 ℃ for 1h, keeping the temperature at 280 ℃ for 1h, and keeping the temperature at 300 ℃ for 1 h.
4. The method for preparing biological oleic acid from cottonseed oil and saponin as claimed in claim 1, wherein the hydrogen pressure in S1 is 3Mpa, and the space velocity is 2h-1The hydrogen-oil ratio was 500.
5. The method for preparing biological oleic acid from cottonseed oil saponin as claimed in claim 1, wherein S2 is specifically as follows: heating cottonseed oil to 80 ℃, adding methanol and a pre-ester catalyst, stirring vigorously, reacting for 1-2h under the condition of reflux, cooling and stopping the reaction, standing and layering reactants, taking an upper layer mixture, and distilling under reduced pressure to obtain the pre-esterified cottonseed oil.
6. The method for preparing biological oleic acid from cottonseed oil and saponin as claimed in claim 1, wherein the hydrogen pressure in S3 is 3Mpa, the temperature is 320 ℃, and the space velocity is 2h-1The hydrogen-oil ratio was 500.
7. The method for preparing biological oleic acid from cottonseed oil and saponin as claimed in claim 5, characterized in that the pre-ester catalyst is prepared by the following method: mixing TiCl4Slowly adding into distilled water, adding 28% wt ammonia water under strong stirring until the pH of the solution is 9-10, standing and aging at-5 deg.C for 24 hr, filtering, and washing until no Cl is formed-Drying at 110 ℃ for 24h to obtain Ti (OH)4A mixture of Ti (OH)4Is placed at 0.5-1.5mol/L (NH4)2S2O8After being soaked for 4-6h, the mixture is dried and roasted at 425-575 ℃.
CN202111408744.3A 2021-11-25 2021-11-25 Preparation method of cottonseed oil and saponin biological oleic acid Pending CN114196481A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111408744.3A CN114196481A (en) 2021-11-25 2021-11-25 Preparation method of cottonseed oil and saponin biological oleic acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111408744.3A CN114196481A (en) 2021-11-25 2021-11-25 Preparation method of cottonseed oil and saponin biological oleic acid

Publications (1)

Publication Number Publication Date
CN114196481A true CN114196481A (en) 2022-03-18

Family

ID=80648858

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111408744.3A Pending CN114196481A (en) 2021-11-25 2021-11-25 Preparation method of cottonseed oil and saponin biological oleic acid

Country Status (1)

Country Link
CN (1) CN114196481A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101074390A (en) * 2007-07-19 2007-11-21 杨庆利 Production of biological diesel oil by high-acid value grease
CN101230309A (en) * 2008-01-11 2008-07-30 四川大学 Method for preparing biodiesel by lowering value of high acid palm oil
CN103571546A (en) * 2012-07-31 2014-02-12 青岛嘉能节能环保技术有限公司 Method for preparing biodiesel by catalyzing cottonseed oil by solid alkali
CN106944112A (en) * 2017-03-16 2017-07-14 济南大学 One kind is used for high acid value waste oil fat pre-esterification solid acid catalyst
CN110511823A (en) * 2019-07-17 2019-11-29 臧树良 A method of second generation biodiesel is prepared with food processing waste oil

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101074390A (en) * 2007-07-19 2007-11-21 杨庆利 Production of biological diesel oil by high-acid value grease
CN101230309A (en) * 2008-01-11 2008-07-30 四川大学 Method for preparing biodiesel by lowering value of high acid palm oil
CN103571546A (en) * 2012-07-31 2014-02-12 青岛嘉能节能环保技术有限公司 Method for preparing biodiesel by catalyzing cottonseed oil by solid alkali
CN106944112A (en) * 2017-03-16 2017-07-14 济南大学 One kind is used for high acid value waste oil fat pre-esterification solid acid catalyst
CN110511823A (en) * 2019-07-17 2019-11-29 臧树良 A method of second generation biodiesel is prepared with food processing waste oil

Similar Documents

Publication Publication Date Title
Sarin Biodiesel: production and properties
CN100491503C (en) Process of preparing biological diesel
CN101418225A (en) Method for preparing biodiesel by using supported solid acid combining cosolvent
Kadapure et al. Optimization of conversion of Pongamia pinnata oil with high FFA to biodiesel using novel deep eutectic solvent
CN101108976B (en) Biological diesel oil and method of manufacturing the same
CN102430427B (en) Catalyst for preparing bio-diesel, preparation method and application thereof
JP2023011537A (en) Catalyst and preparation method of bio-diesel using the catalyst
CN101705155A (en) Method for industrially preparing biological diesel by waste grease
JP7057552B1 (en) A catalyst and a method for producing a biodiesel using this catalyst
Yan et al. Catalytic conversion of triglycerides to liquid biofuels through transesterification, cracking, and hydrotreatment processes
CN100523131C (en) Esterification reaction technique of preparing biodiesel by waste oil
CN114196481A (en) Preparation method of cottonseed oil and saponin biological oleic acid
CN106316727B (en) A kind of porous particulated ammonium oil explosive and preparation method thereof
Dewajani et al. Conversion of Crude Glycerol from by-Product Biodiesel into Bio-additive of Fuel through Acetylation Reaction based on Modified Zeolite Catalyst
KR100447283B1 (en) Manufacturing method of biodiesel fuel using animal fats
CN106190591A (en) The esterification of a kind of biodiesel, ester exchange reaction method
CN108841422A (en) A kind of hybrid diesel fuel and preparation method thereof
CN101173175A (en) Method for producing biological diesel oil with waste propagation oil and fat
CN102631911B (en) Hydrophobic solid base catalyst and method for synthesizing biodiesel from grease containing water and free fatty acids
CN110871084A (en) Non-supported hydrodeoxygenation catalyst and preparation method thereof
Ramírez-Arias et al. Biodiesel synthesis: use of activated carbon as support of the catalysts
CN108795513B (en) Corrosion-resistant expansion-inhibiting water-resistant methanol gasoline
CN108295834B (en) Efficient and stable core-shell CeO for producing biodiesel2@ CaO catalyst and application thereof
CN1283765C (en) Method for producing biological clean fuel
CN108179050B (en) Cetane number improver, production process and application

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20220505

Address after: 843000 Aksu economic and Technological Development Zone, Aksu Prefecture, Xinjiang Uygur Autonomous Region (Xiyuan Zhejiang Industrial Park)

Applicant after: Aksu harluk Biotechnology Co.,Ltd.

Address before: 843000 No. 01, yard of Aksu harluk Biotechnology Co., Ltd., Xihu Road, Aksu economic and Technological Development Zone, Aksu Prefecture, Xinjiang Uygur Autonomous Region

Applicant before: Xinjiang Huaxiong Renewable Resources Technology Co.,Ltd.