CN106753814A - A kind of low-sulfur, the production method without sulphur, high ester content biodiesel - Google Patents

A kind of low-sulfur, the production method without sulphur, high ester content biodiesel Download PDF

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Publication number
CN106753814A
CN106753814A CN201710122278.XA CN201710122278A CN106753814A CN 106753814 A CN106753814 A CN 106753814A CN 201710122278 A CN201710122278 A CN 201710122278A CN 106753814 A CN106753814 A CN 106753814A
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CN
China
Prior art keywords
methyl alcohol
biodiesel
water content
content
sulphur
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Pending
Application number
CN201710122278.XA
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Chinese (zh)
Inventor
冀星
吕勃
崔建志
张钰
王继刚
李里虎
王书平
冀旌语
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Yunnan Ying Ding Bio Energy Ltd By Share Ltd
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Yunnan Ying Ding Bio Energy Ltd By Share Ltd
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Priority to CN201710122278.XA priority Critical patent/CN106753814A/en
Publication of CN106753814A publication Critical patent/CN106753814A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • 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
    • C10G3/42—Catalytic treatment
    • 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
    • C10G7/00—Distillation of hydrocarbon oils
    • C10G7/04—Dewatering
    • 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
    • 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
    • C10G2300/1003—Waste materials
    • C10G2300/1007—Used oils
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • 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
    • 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 invention belongs to petrochemical industry, new energy, the comprehensive utilization of discarded grease, production of biodiesel, fine chemistry industry, green chemical industry, organic synthesis field, and in particular to a kind of low-sulfur, the production method without sulphur, high ester content biodiesel.The present invention provides a kind of low-sulfur, the production method without sulphur, high ester content biodiesel, and water content methyl alcohol higher is separated from reaction system, individually dehydration, is carried out when being dehydrated different under two environment from reaction system；And controlling reaction temperature be 50 DEG C 70 DEG C between, avoided the formation of on the premise of reaction rate is not sacrificed oil sulfonation and other side reactions.Products obtained therefrom is through national oil petroleum chemicals Quality Supervision and Inspection Center（Guangdong）Detected, testing result is：Sulfur content is 7.3mg/kg, and ester content is 96.6%, and survey report numbering is：No.201701398.This result is better than《Diesel fuel blending biodiesel（BD100）》（GB/T20828‑2015）.

Description

A kind of low-sulfur, the production method without sulphur, high ester content biodiesel
Technical field
The invention belongs to petrochemical industry, new energy, the comprehensive utilization of discarded grease, production of biodiesel, fine chemistry industry, green Chemical industry, organic synthesis field, and in particular to a kind of low-sulfur, the production method without sulphur, high ester content biodiesel.
Background technology
Biodiesel refers to by waste oils and fatses ester（Ester fat acid glycerol three ester）, ester fat acid and alcohol（Methyl alcohol or ethanol）Through Esterification, ester exchange reaction obtain being ester fatty acid methyl esters or ester fat acetoacetic ester.To realize comprehensive utilization of resources, waste oil, acid are commonly used The discarded grease such as carburetion, swill oil replaces edible grease and methyl alcohol reaction.Contain moisture in discarded grease, discard grease and methyl alcohol Reaction is needed in the environment of temperature is for 70 DEG C -110 DEG C, and the moisture of reaction generation is taken away in methyl alcohol evaporation.Tradition reaction exist with Lower defect：
One is high energy consumption；
Two is that the moisture that reaction is generated can be blended in biodiesel and glycerine, is to take these moisture out of reaction system, it is ensured that React is carried out to the reaction of generation methyl esters, generally uses temperature higher, methyl alcohol evaporator strip is walked moisture.Biodiesel is right in itself Methyl alcohol has the solubility of 5%-6%, and the glycerine of generation is infinitely miscible with water, methyl alcohol, as the carrying out of reaction is, it is necessary to improve reaction Temperature just can guarantee that methyl alcohol takes water out of reaction system.
Three is temperature of reaction system high, and the sulphur in catalyst can occur with the double bond in the carbochain in the acid of ester fat and neutral oil Sulfonating reaction, easily dehydration forms dimethyl ether to methyl alcohol, and oil is easily polymerized under the catalysis of acid, and catalyst is susceptible to gather Close, sulfur content is higher during these reactions cause biodiesel, and ester content is relatively low, biodiesel fuel quality is not reached Standard. If reaction temperature is low, reaction rate declines, low production efficiency.
Four is in the prior art using dehydration in system, i.e., methyl alcohol evaporator strip constantly to be walked into moisture in course of reaction, is taken off Water is carried out simultaneously with esterification.This results in that temperature in reaction system is higher, and side reaction is more.
The content of the invention
To solve the problems, such as above technology, the present invention provides a kind of low-sulfur, the life without sulphur, high ester content biodiesel Product method, water content methyl alcohol higher is separated from reaction system, individually dehydration, and dehydration is with reaction system in two environment Carried out when lower different；And controlling reaction temperature be 50 DEG C -70 DEG C between, avoided the formation of on the premise of reaction rate is not sacrificed oil Sulfonation and other side reactions.
Its technical scheme is：
（1）Esterification：By in discarded grease, methyl alcohol and catalyst input reactor, heating makes reaction temperature at 50 DEG C -70 Between DEG C；
（2）Real-time detection：Reaction starts rear, it is necessary to aqueous in the water content and methyl alcohol carried out in real-time detection reaction system Amount；
A. the water content in detection architecture：If the water content in system is more than 10%, aqueous methanol is separated from system, body The outer dehydration of system, will continue to react in the methyl alcohol return system after dehydration；
B. the water content in methyl alcohol is detected：Isolate aqueous methanol, the water content in detection methyl alcohol, if the water content in methyl alcohol is big In 10%, then aqueous methanol is separated from system, be dehydrated outside system, will continue to react in the methyl alcohol return system after dehydration.
The step（2）In, catalyst content is less than 0.3%-0.5% in detection reaction system, then toward supplement in reactor Catalyst.
The catalyst is sulfuric acid, sulfonic acid, benzene sulfonic acid, phosphoric acid, resin.
It is dehydrated outside the system, refers to that water content methyl alcohol higher is separated from reaction system, individually dehydration, is taken off Water is carried out when different under two environment from reaction system.
There is contact in the water content in the water content and reactor bottom methyl alcohol in system, when the water content in system is exceeded When, methyl alcohol water content must be exceeded, is required for separating aqueous methanol from system, be dehydrated outside system.
It is on the premise of ensureing oil and methyl alcohol reaction rate, ensureing production efficiency, to produce low-sulfur, without sulphur, ester biological high Diesel oil, inventor have passed through many experiments, and products obtained therefrom is through national oil petroleum chemicals Quality Supervision and Inspection Center（Guangdong）Enter Row detects that testing result is：Sulfur content is 7.3mg/kg, and ester content is 96.6%, and survey report numbering is： No.201701398.This result is better than《Diesel fuel blending biodiesel（BD100）》（GB/T20828-2015）.
Beneficial effects of the present invention：
（1）The reaction temperature of the inventive method be 50 DEG C -70 DEG C, reduce reaction temperature, reduce energy consumption, it is therefore prevented that sulfonation with And other side reactions；
（2）In the reaction of the inventive method, while the water content in water content and methyl alcohol in real-time detection system, reaction system Outer dehydration, without the reaction in influence system；
（3）Method of the inventive method using being dehydrated outside system, water content methyl alcohol higher is separated from reaction system, Individually dehydration, is carried out when being dehydrated different under two environment from reaction system；The polymerization of oil and being polymerized for catalyst are prevented, effectively Improve biodiesel production rate.
Brief description of the drawings
Fig. 1 is low-sulfur, the production technology figure without sulphur, high ester content biodiesel；
Fig. 2 is national oil petroleum chemicals Quality Supervision and Inspection Center（Guangdong）The scanned copy of the examining report for being detected（Inspection Testing report number is： No.201701398）.
Specific embodiment
Example 1
A kind of low-sulfur, the production method without sulphur, high ester content biodiesel, it is characterised in that comprise the following steps：
（1）Esterification：By in discarded grease, methyl alcohol and catalyst input reactor, heating makes reaction temperature at 50 DEG C；
（2）Real-time detection：Reaction starts rear, it is necessary to aqueous in the water content and methyl alcohol carried out in real-time detection reaction system Amount；
A. the water content in detection architecture：If the water content in system is more than 10%, aqueous methanol is separated from system, body The outer dehydration of system, will continue to react in the methyl alcohol return system after dehydration；
B. the water content in methyl alcohol is detected：Isolate aqueous methanol, the water content in detection methyl alcohol, if the water content in methyl alcohol is big In 10%, then aqueous methanol is separated from system, be dehydrated outside system, will continue to react in the methyl alcohol return system after dehydration.
The step（2）In, catalyst content is less than 0.3% in detection reaction system, then toward supplement catalysis in reactor Agent.
The catalyst is sulfuric acid.
It is dehydrated outside the system, refers to that water content methyl alcohol higher is separated from reaction system, individually dehydration, is taken off Water is carried out when different under two environment from reaction system.
Embodiment 2
A kind of low-sulfur, the production method without sulphur, high ester content biodiesel, comprise the following steps：
（1）Esterification：By in discarded grease, methyl alcohol and catalyst input reactor, heating makes reaction temperature at 70 DEG C；
（2）Real-time detection：Reaction starts rear, it is necessary to aqueous in the water content and methyl alcohol carried out in real-time detection reaction system Amount；
A. the water content in detection architecture：If the water content in system is more than 10%, aqueous methanol is separated from system, body The outer dehydration of system, will continue to react in the methyl alcohol return system after dehydration；
B. the water content in methyl alcohol is detected：Isolate aqueous methanol, the water content in detection methyl alcohol, if the water content in methyl alcohol is big In 10%, then aqueous methanol is separated from system, be dehydrated outside system, will continue to react in the methyl alcohol return system after dehydration.
The step（2）In, catalyst content is less than 0.5% in detection reaction system, then toward supplement catalysis in reactor Agent.
The catalyst is phosphoric acid or resin.
It is dehydrated outside the system, refers to that water content methyl alcohol higher is separated from reaction system, individually dehydration, is taken off Water is carried out when different under two environment from reaction system.

Claims (4)

1. a kind of low-sulfur, the production method without sulphur, high ester content biodiesel, it is characterised in that comprise the following steps：
（1）Esterification：By in discarded grease, methyl alcohol and catalyst input reactor, heating makes reaction temperature at 50 DEG C -70 Between DEG C；
（2）Real-time detection：Reaction starts rear, it is necessary to aqueous in the water content and methyl alcohol carried out in real-time detection reaction system Amount；
A. the water content in detection architecture：If the water content in system is more than 10%, aqueous methanol is separated from system, body The outer dehydration of system, will continue to react in the methyl alcohol return system after dehydration；
B. the water content in methyl alcohol is detected：Isolate aqueous methanol, the water content in detection methyl alcohol, if the water content in methyl alcohol is big In 10%, then aqueous methanol is separated from system, be dehydrated outside system, will continue to react in the methyl alcohol return system after dehydration.
2. a kind of low-sulfur according to claim 1, the production method without sulphur, high ester content biodiesel, it is characterised in that The step（2）In, catalyst content is less than 0.3%-0.5% in detection reaction system, then toward supplementing catalyst in reactor.
3. a kind of low-sulfur according to claim 1, the production method without sulphur, high ester content biodiesel, it is characterised in that The catalyst is sulfuric acid, sulfonic acid, benzene sulfonic acid, phosphoric acid, resin.
4. a kind of low-sulfur according to claim 1, the production method without sulphur, high ester content biodiesel, it is characterised in that It is dehydrated outside the system, refers to that water content methyl alcohol higher is separated from reaction system, individually dehydration, is dehydrated and reaction System is carried out when different under two environment.
CN201710122278.XA 2017-03-03 2017-03-03 A kind of low-sulfur, the production method without sulphur, high ester content biodiesel Pending CN106753814A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112646664A (en) * 2019-10-12 2021-04-13 常州市金坛区维格生物科技有限公司 Method for preparing low-sulfur biodiesel from acidized oil

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1995288A (en) * 2006-12-25 2007-07-11 昆明理工大学 Process for preparing biodiesel oil
CN101225322A (en) * 2008-02-18 2008-07-23 中国科学院海洋研究所 Method for producing biodiesel by using seaside mallow seed kernel oil
CN101641429A (en) * 2007-03-14 2010-02-03 恩迪科特生物燃料Ⅱ有限责任公司 The production of low glycerine low-sulfur biodiesel fuel
CN101768517A (en) * 2010-01-28 2010-07-07 华中农业大学 Preparation method of biodiesel
CN103540412A (en) * 2007-03-14 2014-01-29 恩迪科特生物燃料Ii有限责任公司 Production of biodiesel fuels which are low in glycerin and sulfur
CN104673502A (en) * 2015-02-03 2015-06-03 江苏西方环保科技有限公司 Continuous esterification technique for producing biodiesel from waste grease

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1995288A (en) * 2006-12-25 2007-07-11 昆明理工大学 Process for preparing biodiesel oil
CN101641429A (en) * 2007-03-14 2010-02-03 恩迪科特生物燃料Ⅱ有限责任公司 The production of low glycerine low-sulfur biodiesel fuel
CN103540412A (en) * 2007-03-14 2014-01-29 恩迪科特生物燃料Ii有限责任公司 Production of biodiesel fuels which are low in glycerin and sulfur
CN101225322A (en) * 2008-02-18 2008-07-23 中国科学院海洋研究所 Method for producing biodiesel by using seaside mallow seed kernel oil
CN101768517A (en) * 2010-01-28 2010-07-07 华中农业大学 Preparation method of biodiesel
CN104673502A (en) * 2015-02-03 2015-06-03 江苏西方环保科技有限公司 Continuous esterification technique for producing biodiesel from waste grease

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112646664A (en) * 2019-10-12 2021-04-13 常州市金坛区维格生物科技有限公司 Method for preparing low-sulfur biodiesel from acidized oil

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Application publication date: 20170531