CN107459997A - A kind of high acid value waste oil glycerine is without catalytic esterification deacidification continuous production technology - Google Patents
A kind of high acid value waste oil glycerine is without catalytic esterification deacidification continuous production technology Download PDFInfo
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- CN107459997A CN107459997A CN201710598802.0A CN201710598802A CN107459997A CN 107459997 A CN107459997 A CN 107459997A CN 201710598802 A CN201710598802 A CN 201710598802A CN 107459997 A CN107459997 A CN 107459997A
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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
- C10G3/40—Thermal non-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
- 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
For a kind of high acid value waste oil glycerine without catalytic esterification deacidification continuous production technology, step includes raw material mixing dispatching, mixed material exchanges heat with finished product, mixed material preheating, mixed material flash-evaporation dehydration, serialization esterification after heat exchange, separates the glycerine extracted out in esterification process.The present invention, which efficiently solves, prepares that esterification speed caused by biodiesel pre-esterification deacidification in time can not be separated reaction water using methanol as esterifying agent because reaction temperature is low is slow, the halfway problem of esterification with the waste cooking oil of high acid value, oil prodution industry leftover bits and pieces, and added in esterification process sulfuric acid as equipment corrosion caused by catalyst with generation a large amount of spent acid environmental pollution by water the problem of.Esterification uses continuous production technology, and the heat exchange of raw material and finished product is realized in continuous process, and frequent operation caused by solving the problems, such as batch esterification technique is complicated, recruitment cost is high, energy consumption is high and the small efficiency of yield is low.
Description
Technical field
The present invention is to prepare biodiesel pre-esterification deacidification technique, category by the use of the high acid value waste oil of low cost as raw material
In discarded object recycling, recycling economy field.More particularly to a kind of energy-saving efficient high acid value waste oil glycerine without catalytic esterification
Deacidification continuous production technology.
Background technology
Increasingly reduced with the deposit of traditional fossil energy, novel renewable energy is increasingly taken seriously, biodiesel
As a kind of substitute of petrifaction diesel, because of its excellent performance and environment friendly by the common concern of countries in the world.
Biodiesel is as reproducible clean energy resource, and to environmental protection, reduce the dependence to oil has Developing Biodiesel
Significance.
Biodiesel is the fatty acid methyl ester that is process by ester exchange reaction using animal and plant fat as raw material（FAME）
Or ethyl ester fuel（FAEE）.During production of biodiesel, cost of material accounts for 70% of total cost of production or so, therefore raw material
Price be determine biodiesel cost principal element, be production of biodiesel enterprise profit restrict point.Due to Chinese people
Mouthful numerous, grain demand is big, in order to realize the demand for development of " grain not being striven with people, do not strive ground with grain ", no image of Buddha American-European countries that
Sample is largely using the edible oil and fat such as genetically engineered soybean rapeseed oil production biodiesel.But China is edible oil and fat consumption big country,
The yield of food and beverage waste oil and grease is very big, accounts for the 20%~30% of edible oil and fat aggregate consumption, with Chinese average annual consumption edible oil and fat
21000000 tons of meters, it is annual to produce food and beverage waste oil and grease 400~6,000,000 ton, while China is commercial grease processing big country again, is often produced per year
Raw greasyfoot, the millions of tons of gleditsia sinensis.If these food and beverage waste oil and greases and commercial grease leftover bits and pieces, gleditsia sinensis directly discharge,
Environment and water pollution are not only caused, and is also a kind of serious wasting of resources.In order to thoroughly solve waste in-ore rate and industry
Greasyfoot endangers to caused by environment, improves its value, and find new utilization ways turns into the task of top priority.It is discarded
Animal and plant fat and oil prodution industry leftover bits and pieces have the advantages such as cheap, wide material sources, utilize it as raw material and prepare biology
Diesel oil, there is good development prospect, be the primary raw material that our biodiesel enterprises prepare biodiesel.
But food and beverage waste oil and grease and commercial grease leftover bits and pieces all have very high acid number, cannot be used directly for ester exchange and prepare fat
Fatty acid methyl esters.At present, biodiesel is prepared using high acid value waste oil as raw material and uses two-step method, be i.e. acid catalyzed esterification depickling is pre-
After processing, then with base-catalyzed transesterification biodiesel is prepared, during esterification deacidification, the most frequently used esterifying agent is methanol, esterification
Reaction temperature only has 70 DEG C, and below the boiling point of water, the water of esterification generation is maintained in reactor, is unfavorable for being esterified
The progress of reaction, causing depickling speed, relatively time-consuming slowly, is typically easily caused using sulfuric acid as catalyst to the serious of equipment
Corrosion, and produce a large amount of spent acid environmental pollution by water, and methanol usage is big, methanol is aqueous needs to take off by rectifying for separation after esterification
Water, production cost is high, and production efficiency is low.
Using food and beverage waste oil and grease, oil prodution industry leftover bits and pieces as raw material, develop a kind of energy-saving and environmental protection, efficiently reduce its acid number
To meet that the technique tool for preparing the requirement of biodiesel ester exchange reaction is of great significance.The present invention is using glycerine as ester
Agent, without adding catalyst in the case of by the aliphatic acid in grease and glycerine, the production of serialization esterification is sweet at high temperature
Grease come reduce waste oil acid number with meet prepare biodiesel ester exchange requirement, there is advantages below, glycerine is both raw material
The accessory substance during production of biodiesel again, to its appropriate purification process can cycling and reutilization, in addition compared with methanol,
Glycerine boiling point is high, need not flow back during esterification, the water of esterification generation can directly vacuum detach, be advantageous to esterification instead
Should the positive speed for carrying out, accelerating esterification so that the acid value of oil and fat after esterification drops must be than more thoroughly, after over-churning
Acid value of oil and fat can drop to below 2mgKOH/g, be fully able to meet the requirement for preparing biodiesel ester exchange.
The content of the invention
The technical problem of solution：It is an object of the invention to provide a kind of energy-saving efficient high acid value waste oil glycerine without catalysis
Esterification acid reduction continuous production technology, efficiently solve and biological bavin is prepared with the waste cooking oil of high acid value, oil prodution industry leftover bits and pieces
Reaction water can not be separated caused esterification by oily pre-esterification deacidification in time using methanol as esterifying agent because reaction temperature is low
Speed is slow, the halfway problem of esterification, and sulfuric acid is added in esterification process as equipment corrosion caused by catalyst and generation
The problem of a large amount of spent acid environmental pollution by water.Esterification uses continuous production technology, and raw material is realized in continuous process
With the heat exchange of finished product, frequent operation caused by solving batch esterification technique is complicated, recruitment cost is high, energy consumption height with
And the small efficiency of yield it is low the problem of.
Technical scheme：A kind of high acid value waste oil glycerine is without catalytic esterification deacidification continuous production technology, step：Raw material
Mixing dispatching：Raw oil material and glycerine are preheated to 40 DEG C, with pump blending transportation to heat exchanger；Mixed material exchanges heat with finished product：
Mixed material and finished product adverse current pass through two tubular heat exchanger heat-shifts, and mixed material series connection exchanges heat by two shell and tubes
Device shell side is heated, and the series connection of finished product grease is cooled by two shell and tube tube sides；Mixed material preheats after heat exchange：After exchanging heat
Mixed material heats by preheater；Mixed material flash-evaporation dehydration：Mixed material after preheating is sloughed by flash vacuum extracting
Free Free water therein；Serialization esterification：Mixed material low in and high out automatic overflow series connection after flash distillation is passed through successively
Four reaction kettle of the esterification, lasting stirring, vacuum extract the water of esterification generation out, and the finished product after esterification is defeated by transition tank pump
Heat exchanger is delivered to, finished pot is entered after heat exchange, on-line period measures the finished product acid number after the 4th esterifying kettle esterification；Separation
The glycerine extracted out in esterification process：The esterification water extracted out in esterification process and glycerine mixed vapour are passed through into rectifying online
Tower, the glycerine that vacuum is extracted out is reclaimed out, tower top waste water is collected by condenser cooling, and the glycerine of recovery is directly used in production
Raw material.
Above-mentioned raw materials grease is that the high acid value propagation waste oil fat for removing water is stood by removal of impurities, acid value of oil and fat 5~
190mgKOH/g, glycerine are the industry glycerol that content is not less than 95wt.%.
Above-mentioned propagation waste oil fat is at least one of gutter oil, hogwash fat, acidification oil, commercial grease leftover bits and pieces.
The glycerine of above-mentioned input is the 10%~15% of grease gross mass.
Above-mentioned mixed material is heated to 100~130 DEG C after heat exchanger exchanges heat, finished product grease temperature after heat exchange
130~150 DEG C are down to by 235 DEG C.
Above-mentioned preheater uses tubular heat exchanger, and heating medium, 250 DEG C of heat conduction oil temperature, preheating are used as using conduction oil
Grease temperature afterwards is 200 DEG C.
Above-mentioned mixed material vacuum flashing dehydration temperaturre is 200 DEG C, and vacuum is -0.03~-0.05MPa.
Above-mentioned four esterifying kettle temperature of serialization esterification are respectively 210 DEG C, 220 DEG C, 230 DEG C, 235 DEG C；Above three
Individual esterifying kettle glycerol content is high, is the 5%~10% of total oil quantity, vacuum is -0.03~-0.05MPa, and the 4th reactor is true
Reciprocal of duty cycle is -0.05~-0.08MPa；Four esterifying kettle mixing speeds are 89r/m；Four reaction kettle of the esterification use coil tube type heating
Mode, using conduction oil as heating medium, heat conduction oil temperature be 250 DEG C, by four esterifying kettles mixed material using it is low enter height
The mode for going out automatic overflow is connected；The measure of acid value of oil and fat is with reference to national standard GBT 5530-2005 animal and plant fat acid numbers after esterification
With the assay method of acidity.
105 DEG C of the glycerine rectifying tower top temperature that vacuum is taken out of in above-mentioned rectifying column separation esterification process, bottom temperature 150
DEG C, vacuum is -0.03~-0.05MPa.
Beneficial effect：The present invention provides a kind of energy-saving efficient high-acid value grease glycerine without the continuous metaplasia of catalytic esterification deacidification
Production. art, efficiently solve makes it with the waste cooking oil of high acid value, oil prodution industry leftover bits and pieces preparation biodiesel pre-esterification deacidification
Reach the problem of preparing biodiesel ester exchange requirement, there is following remarkable advantage：
（1）The present invention is using the conventional methanol of glycerine replacement as esterifying agent, and glycerine is both raw material and production of biodiesel process
In accessory substance, to its appropriate purification process can cycling and reutilization, glycerine boiling point is high, need not flow back during esterification, ester
Change reaction generation water can directly vacuum detach, be advantageous to the positive progress of esterification, accelerate the speed of esterification, make
Acid value of oil and fat after must being esterified drops must be than more thoroughly, the acid value of oil and fat after over-churning can drop to below 2mgKOH/g, completely
It disclosure satisfy that the requirement for preparing biodiesel ester exchange.
（2）The present invention is not required to add any catalyst, and avoid methanol needs to add sulfuric acid as catalysis as esterifying agent
The problem of equipment corrosion caused by agent and generation a large amount of spent acid environmental pollution by water.
（3）Present invention employs the production technology of serialization, whole course of reaction series connection continuous feed continuous discharge, operation
Simply, conveniently, recruitment cost is low, the big efficiency high of output.
（4）The present invention is using the technique of raw material and finished product countercurrent flow, and substantially increasing charging reduces energy consumption, section
About production cost.
（5）The glycerine that the present invention is taken out of using vacuum extraction water in online rectifying separation esterification process, has been reclaimed sweet
Oil, waste water COD concentration is reduced, saved the cost of processing waste water, while online rectifying separation saves without additionally supplementing energy
About a large amount of energy consumptions, reach purpose that is energy-saving, saving production finished product.
Brief description of the drawings
Fig. 1 is a kind of energy-saving efficient high acid value waste oil glycerine of the present invention without catalytic esterification deacidification continuous production technology
Process chart.
Embodiment
Following examples only technical concepts and features to illustrate the invention, its object is to allow person skilled in the art
It is that can understand present disclosure and implement according to this, it is not intended to limit the scope of the present invention.It is all according to the present invention
The equivalent transformation or modification that Spirit Essence is done, should all be included within the scope of the present invention.
Embodiment 1
（1）Raw material mixing dispatching：By acid number be 12 tons/h of 48mgKOH/g raw oil materials and content is 95.7% 1.32 tons/h of glycerine
Mixed respectively by centrifugal pump conveying after flowmeter measures into heat exchanger, glycerine and oil quality ratio are 1.1：10.
（2）Mixed material exchanges heat with finished product：Mixed material and finished product adverse current pass through two tubular heat exchanger heat-shifts,
Mixed material series connection is heated by two tubular heat exchanger shell sides, and the series connection of finished product grease is dropped by two shell and tube tube sides
Temperature.Mixed material is heated to 116 DEG C after heat exchange, and finished product grease temperature after heat exchange is down to 142 DEG C by 235 DEG C.
（3）Mixed material preheats after heat exchange：Mixed material heats by preheater after exchanging heat, and is heated to 200 DEG C.
（4）Mixed material flash-evaporation dehydration：Mixed material after preheating sloughs therein dissociate certainly by flash vacuum extracting
By water, vacuum flashing dehydration temperaturre is 200 DEG C, and vacuum is -0.03MPa.
（5）Serialization esterification：Four esters are passed through in mixed material low in and high out automatic overflow series connection after flash distillation successively
Change reactor, lasting stirring, vacuum extracts the water of esterification generation out.Four esterifying kettle temperature are respectively 210 DEG C, 220 DEG C,
230℃、235℃.Above three esterifying kettle vacuums are -0.03MPa, and the 4th reactor vacuum is -0.05MPa.Four
Esterifying kettle mixing speed is 89r/m, esterifying kettle volume 20m3.Four reaction kettle of the esterification use coil tube type heating mode, with heat conduction
Oil is heating medium, and heat conduction oil temperature is 250 DEG C.Finished product grease after esterification is delivered to heat exchanger by transition tank with pump to be passed through
Enter finished pot after heat exchange.On-line period measures the finished product acid number after the 4th esterifying kettle esterification, acid number 1.86mgKOH/g.
（6）The glycerine extracted out in separation esterification process：The esterification water and glycerine extracted out in esterification process are mixed and steamed
Vapour passes through rectifying column online, and 105 DEG C of rectifying column tower top temperature, 150 DEG C of bottom temperature, vacuum is -0.03MPa, and vacuum is taken out
The glycerine gone out is reclaimed out, and tower top waste water is collected by condenser cooling, and the glycerine of recovery is directly used in raw materials for production.
Embodiment 2
（1）Raw material mixing dispatching：By acid number be 13 tons/h of 26mgKOH/g raw oil materials and content is distinguished for 96% 1.3 tons/h of glycerine
Mixed by centrifugal pump conveying after flowmeter measures into heat exchanger, the mass ratio of glycerine and grease is 1:10.
（2）Mixed material exchanges heat with finished product：Mixed material and finished product adverse current pass through two tubular heat exchanger heat-shifts,
Mixed material series connection is heated by two tubular heat exchanger shell sides, and the series connection of finished product grease is dropped by two shell and tube tube sides
Temperature.Mixed material is heated to 110 DEG C after heat exchange, and finished product grease temperature after heat exchange is down to 148 DEG C by 235 DEG C.
（3）Mixed material preheats after heat exchange：Mixed material heats by preheater after exchanging heat, and is heated to 200 DEG C.
（4）Mixed material flash-evaporation dehydration：Mixed material after preheating sloughs therein dissociate certainly by flash vacuum extracting
By water, vacuum flashing dehydration temperaturre is 200 DEG C, and vacuum is -0.03MPa.
（5）Serialization esterification：Four esters are passed through in mixed material low in and high out automatic overflow series connection after flash distillation successively
Change reactor, lasting stirring, vacuum extracts the water of esterification generation out.Four esterifying kettle temperature are respectively 210 DEG C, 220 DEG C,
230℃、235℃.Above three esterifying kettle vacuums are -0.03MPa, and the 4th reactor vacuum is -0.05MPa.Four
Esterifying kettle mixing speed is 89r/m, esterifying kettle volume 20m3.Four reaction kettle of the esterification use coil tube type heating mode, with heat conduction
Oil is heating medium, and heat conduction oil temperature is 250 DEG C, and the finished product grease after esterification is delivered to heat exchanger by transition tank with pump to be passed through
Enter finished pot after heat exchange.On-line period measures the finished product acid number after the 4th esterifying kettle esterification, acid number 1.73mgKOH/g.
（6）The glycerine extracted out in separation esterification process：The esterification water and glycerine extracted out in esterification process are mixed and steamed
Vapour passes through rectifying column online, and 105 DEG C of rectifying tower top temperature, 150 DEG C of bottom temperature, vacuum is -0.03MPa.Vacuum is extracted out
Glycerine reclaim out, tower top waste water is collected by condenser cooling, and the glycerine of recovery is directly used in raw materials for production.
Embodiment 3
（1）Raw material mixing dispatching：By acid number be 11 tons/h of 71mgKOH/g raw oil materials and content is 96.1% 1.32 tons/h of glycerine
Mixed respectively by centrifugal pump conveying after flowmeter measures into heat exchanger, the mass ratio of glycerine and grease is 1.2:
10。
（2）Mixed material exchanges heat with finished product：Mixed material and finished product adverse current pass through two tubular heat exchanger heat-shifts,
Mixed material series connection is heated by two tubular heat exchanger shell sides, and the series connection of finished product grease is dropped by two shell and tube tube sides
Temperature.Mixed material is heated to 122 DEG C after heat exchange, and finished product grease temperature after heat exchange is down to 137 DEG C by 235 DEG C.
（3）Mixed material preheats after heat exchange：Mixed material heats by preheater after exchanging heat, and is heated to 200 DEG C.
（4）Mixed material flash-evaporation dehydration：Mixed material after preheating sloughs therein dissociate certainly by flash vacuum extracting
By water, vacuum flashing dehydration temperaturre is 200 DEG C, and vacuum is -0.04MPa.
（5）Serialization esterification：Four esters are passed through in mixed material low in and high out automatic overflow series connection after flash distillation successively
Change reactor, lasting stirring, vacuum extracts the water of esterification generation out.Four esterifying kettle temperature are respectively 210 DEG C, 220 DEG C,
230℃、235℃.Above three esterifying kettle vacuums are -0.04MPa, and the 4th reactor vacuum is -0.06MPa.Four
Esterifying kettle mixing speed is 89r/m, esterifying kettle volume 20m3, four reaction kettle of the esterification use coil tube type heating mode, with heat conduction
Oil is heating medium, and heat conduction oil temperature is 250 DEG C, and the finished product grease after esterification is delivered to heat exchanger by transition tank with pump to be passed through
Enter finished pot after heat exchange.On-line period measures the finished product acid number after the 4th esterifying kettle esterification, acid number 1.92mgKOH/g.
（6）The glycerine extracted out in separation esterification process：The esterification water and glycerine extracted out in esterification process are mixed and steamed
Vapour passes through rectifying column online, and 105 DEG C of rectifying tower top temperature, 150 DEG C of bottom temperature, vacuum is -0.04MPa.Vacuum is extracted out
Glycerine reclaim out, tower top waste water is collected by condenser cooling, and the glycerine of recovery is directly used in raw materials for production.
Embodiment 4
（1）Raw material mixing dispatching：By acid number be 10 tons/h of 95mgKOH/g raw oil materials and content is 1.3 tons/h points of 95.8% glycerine
Mixed by centrifugal pump conveying after flowmeter measures into heat exchanger, the mass ratio of glycerine and grease is 1.3：:10.
（2）Mixed material exchanges heat with finished product：Mixed material and finished product adverse current pass through two tubular heat exchanger heat-shifts,
Mixed material series connection is heated by two tubular heat exchanger shell sides, and the series connection of finished product grease is dropped by two shell and tube tube sides
Temperature.Mixed material is heated to 122 DEG C after heat exchange, and finished product grease temperature after heat exchange is down to 137 DEG C by 235 DEG C.
（3）Mixed material preheats after heat exchange：Mixed material heats by preheater after exchanging heat, and is heated to 200 DEG C.
（4）Mixed material flash-evaporation dehydration：Mixed material after preheating sloughs therein dissociate certainly by flash vacuum extracting
By water, vacuum flashing dehydration temperaturre is 200 DEG C, and vacuum is -0.04MPa.
（5）Serialization esterification：Four esters are passed through in mixed material low in and high out automatic overflow series connection after flash distillation successively
Change reactor, lasting stirring, vacuum extracts the water of esterification generation out.Four esterifying kettle temperature are respectively 210 DEG C, 220 DEG C,
230℃、235℃.Above three esterifying kettle vacuums are -0.04MPa, and the 4th reactor vacuum is -0.07MPa.Four
Esterifying kettle mixing speed is 89r/m, esterifying kettle volume 20m3.Four reaction kettle of the esterification use coil tube type heating mode, with heat conduction
Oil is heating medium, and heat conduction oil temperature is 250 DEG C, and the finished product grease after esterification is delivered to heat exchanger by transition tank with pump to be passed through
Enter finished pot after heat exchange.On-line period measures the finished product acid number after the 4th esterifying kettle esterification, acid number 1.89mgKOH/g.
（6）The glycerine extracted out in separation esterification process：The esterification water and glycerine extracted out in esterification process are mixed and steamed
Vapour passes through rectifying column online, and 105 DEG C of rectifying tower top temperature, 150 DEG C of bottom temperature, vacuum is -0.04MPa.Vacuum is extracted out
Glycerine reclaim out, tower top waste water is collected by condenser cooling, and the glycerine of recovery is directly used in raw materials for production.
Embodiment 5
（1）Raw material mixing dispatching：By acid number be 9 tons/h of 128mgKOH/g raw oil materials and content is 96.1% 1.26 tons/h of glycerine
Mixed respectively by centrifugal pump conveying after flowmeter measures into heat exchanger, the mass ratio of glycerine and grease is 1.4：
10。
（2）Mixed material exchanges heat with finished product：Mixed material and finished product adverse current pass through two tubular heat exchanger heat-shifts,
Mixed material series connection is heated by two tubular heat exchanger shell sides, and the series connection of finished product grease is dropped by two shell and tube tube sides
Temperature.Mixed material is heated to 124 DEG C after heat exchange, and finished product grease temperature after heat exchange is down to 135 DEG C by 235 DEG C.
（3）Mixed material preheats after heat exchange：Mixed material heats by preheater after exchanging heat, and is heated to 200 DEG C.
（4）Mixed material flash-evaporation dehydration：Mixed material after preheating sloughs therein dissociate certainly by flash vacuum extracting
By water, vacuum flashing dehydration temperaturre is 200 DEG C, and vacuum is -0.05MPa.
（5）Serialization esterification：Four esters are passed through in mixed material low in and high out automatic overflow series connection after flash distillation successively
Change reactor, lasting stirring, vacuum extracts the water of esterification generation out.Four esterifying kettle temperature are respectively 210 DEG C, 220 DEG C,
230℃、235℃.Above three esterifying kettle vacuums are -0.05MPa, and the 4th reactor vacuum is -0.07MPa.Four
Esterifying kettle mixing speed is 89r/m, esterifying kettle volume 20m3.Four reaction kettle of the esterification use coil tube type heating mode, with heat conduction
Oil is heating medium, and heat conduction oil temperature is 250 DEG C, and the finished product grease after esterification is delivered to heat exchanger by transition tank with pump to be passed through
Enter finished pot after heat exchange.On-line period measures the finished product acid number after the 4th esterifying kettle esterification, acid number 1.93mgKOH/g.
（6）The glycerine extracted out in separation esterification process：The esterification water and glycerine extracted out in esterification process are mixed and steamed
Vapour passes through rectifying column online, and 105 DEG C of rectifying tower top temperature, 150 DEG C of bottom temperature, vacuum is -0.05MPa.Vacuum is extracted out
Glycerine reclaim out, tower top waste water is collected by condenser cooling, and the glycerine of recovery is directly used in raw materials for production.
Embodiment 6
（1）Raw material mixing dispatching：By acid number be 8 tons/h of 156mgKOH/g raw oil materials and content is 1.2 tons/h points of 96.1% glycerine
Mixed by centrifugal pump conveying after flowmeter measures into heat exchanger, the mass ratio of glycerine and grease is 1.5：10.
（2）Mixed material exchanges heat with finished product：Mixed material and finished product adverse current pass through two tubular heat exchanger heat-shifts,
Mixed material series connection is heated by two tubular heat exchanger shell sides, and the series connection of finished product grease is dropped by two shell and tube tube sides
Temperature.Mixed material is heated to 127 DEG C after heat exchange, and finished product grease temperature after heat exchange is down to 133 DEG C by 235 DEG C.
（3）Mixed material preheats after heat exchange：Mixed material heats by preheater after exchanging heat, and is heated to 200 DEG C.
（4）Mixed material flash-evaporation dehydration：Mixed material after preheating sloughs therein dissociate certainly by flash vacuum extracting
By water, vacuum flashing dehydration temperaturre is 200 DEG C, and vacuum is -0.05MPa.
（5）Serialization esterification：Four esters are passed through in mixed material low in and high out automatic overflow series connection after flash distillation successively
Change reactor, lasting stirring, vacuum extracts the water of esterification generation out.Four esterifying kettle temperature are respectively 210 DEG C, 220 DEG C,
230℃、235℃.Above three esterifying kettle vacuums are -0.05MPa, and the 4th reactor vacuum is -0.08MPa.Four
Esterifying kettle mixing speed is 89r/m, esterifying kettle volume 20m3.Four reaction kettle of the esterification use coil tube type heating mode, with heat conduction
Oil is heating medium, and heat conduction oil temperature is 250 DEG C, and the finished product grease after esterification is delivered to heat exchanger by transition tank with pump to be passed through
Enter finished pot after heat exchange.On-line period measures the finished product acid number after the 4th esterifying kettle esterification, acid number 1.99mgKOH/g.
（6）The glycerine extracted out in separation esterification process：The esterification water and glycerine extracted out in esterification process are mixed and steamed
Vapour passes through rectifying column online, and 105 DEG C of rectifying tower top temperature, 150 DEG C of bottom temperature, vacuum is -0.05MPa.Vacuum is extracted out
Glycerine reclaim out, tower top waste water is collected by condenser cooling, and the glycerine of recovery is directly used in raw materials for production.
Claims (9)
1. a kind of high acid value waste oil glycerine is without catalytic esterification deacidification continuous production technology, it is characterised in that step is：
（1）Raw material mixing dispatching：Raw oil material and glycerine are preheated to 40 DEG C, with pump blending transportation to heat exchanger；
（2）Mixed material exchanges heat with finished product：Mixed material and finished product adverse current pass through two tubular heat exchanger heat-shifts, mix
Raw material series connection is heated by two tubular heat exchanger shell sides, and the series connection of finished product grease is cooled by two shell and tube tube sides；
（3）Mixed material preheats after heat exchange：Mixed material heats by preheater after exchanging heat；
（4）Mixed material flash-evaporation dehydration：Mixed material after preheating sloughs free Free water therein by flash vacuum extracting；
（5）Serialization esterification：Mixed material low in and high out automatic overflow series connection after flash distillation is anti-by four esterifications successively
Kettle is answered, lasting stirring, vacuum extracts the water of esterification generation out, and the finished product after esterification is delivered to heat exchange by transition tank with pump
Device, enters finished pot after heat exchange, and on-line period measures the finished product acid number after the 4th esterifying kettle esterification；
（6）The glycerine extracted out in separation esterification process：The esterification water extracted out in esterification process and glycerine mixed vapour are existed
Line passes through rectifying column, and the glycerine that vacuum is extracted out is reclaimed out, and tower top waste water is collected by condenser cooling, and the glycerine of recovery is straight
Connect and be used for raw materials for production.
2. for a kind of high acid value waste oil glycerine without catalytic esterification deacidification continuous production technology, it is special according to claim 1
Sign is：The raw oil material is that the high acid value propagation waste oil fat for removing water is stood by removal of impurities, acid value of oil and fat 5~
190mgKOH/g, glycerine are the industry glycerol that content is not less than 95wt.%.
3. for a kind of high acid value waste oil glycerine without catalytic esterification deacidification continuous production technology, it is special according to claim 1
Sign is：The propagation waste oil fat is at least one of gutter oil, hogwash fat, acidification oil, commercial grease leftover bits and pieces.
4. for a kind of high acid value waste oil glycerine without catalytic esterification deacidification continuous production technology, it is special according to claim 1
Sign is：The glycerine of input is the 10%~15% of grease gross mass.
5. for a kind of high acid value waste oil glycerine without catalytic esterification deacidification continuous production technology, it is special according to claim 1
Sign is：The mixed material is heated to 100~130 DEG C after heat exchanger exchanges heat, finished product grease temperature after heat exchange
130~150 DEG C are down to by 235 DEG C.
6. for a kind of high acid value waste oil glycerine without catalytic esterification deacidification continuous production technology, it is special according to claim 1
Sign is：The preheater uses tubular heat exchanger, and heating medium, 250 DEG C of heat conduction oil temperature, after preheating are used as using conduction oil
Grease temperature be 200 DEG C.
7. for a kind of high acid value waste oil glycerine without catalytic esterification deacidification continuous production technology, it is special according to claim 1
Sign is：The mixed material vacuum flashing dehydration temperaturre is 200 DEG C, and vacuum is -0.03~-0.05MPa.
8. for a kind of high acid value waste oil glycerine without catalytic esterification deacidification continuous production technology, it is special according to claim 1
Sign is：Described four esterifying kettle temperature of serialization esterification are respectively 210 DEG C, 220 DEG C, 230 DEG C, 235 DEG C；Above three
Esterifying kettle glycerol content is high, is the 5%~10% of total oil quantity, and vacuum is -0.03~-0.05MPa, the 4th reactor vacuum
Spend for -0.05~-0.08MPa；Four esterifying kettle mixing speeds are 89r/m；Four reaction kettle of the esterification use coil tube type heating side
Formula, it is 250 DEG C by heating medium, heat conduction oil temperature of conduction oil, low in and high out is used by the mixed material of four esterifying kettles
The mode of automatic overflow is connected；After esterification the measure of acid value of oil and fat with reference to national standard GBT 5530-2005 animal and plant fats acid numbers and
The assay method of acidity.
9. for a kind of high acid value waste oil glycerine without catalytic esterification deacidification continuous production technology, it is special according to claim 1
Sign is：105 DEG C of the glycerine rectifying tower top temperature that vacuum is taken out of in the rectifying column separation esterification process, 150 DEG C of bottom temperature,
Vacuum is -0.03~-0.05MPa.
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| CN112159728A (en) * | 2020-09-09 | 2021-01-01 | 湖北天基生物能源科技发展有限公司 | Method for reducing acid value of waste oil by esterification |
| CN112852551A (en) * | 2021-01-25 | 2021-05-28 | 茂名市凯跃特种油剂有限公司 | Acid reducing process for preparing bunker fuel oil by glyceride method |
| CN112980488A (en) * | 2021-02-25 | 2021-06-18 | 中国林业科学研究院林产化学工业研究所 | High-acid-value grease non-catalytic esterification and distillation synchronous deacidification process |
| CN113856579A (en) * | 2021-08-16 | 2021-12-31 | 纽威科技(长沙)有限公司 | Heat exchange process and system for treating liquid substance |
| CN115820342A (en) * | 2022-11-04 | 2023-03-21 | 江苏强林生物能源材料有限公司 | Method for continuously preparing neutral grease for biodiesel without catalyst |
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| CN115820342A (en) * | 2022-11-04 | 2023-03-21 | 江苏强林生物能源材料有限公司 | Method for continuously preparing neutral grease for biodiesel without catalyst |
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Application publication date: 20171212 |