CN203530281U - Device for refining biodiesel by palm oil residues and acid oil - Google Patents
Device for refining biodiesel by palm oil residues and acid oil Download PDFInfo
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- CN203530281U CN203530281U CN201320655834.7U CN201320655834U CN203530281U CN 203530281 U CN203530281 U CN 203530281U CN 201320655834 U CN201320655834 U CN 201320655834U CN 203530281 U CN203530281 U CN 203530281U
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- 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
Abstract
The utility model relates to a device for refining biodiesel by palm oil residues and acid oil. The device comprises a catalytic cracking device, a pre-esterification reaction device, a distillation device, an exhaust gas fuel boiler and a water treatment system. The device for refining the biodiesel by the palm oil residues and the acid oil has the following benefits: the device enables raw oil to contain a large amount of diesel components of olefin and alkane before the pre-esterification reaction through the cracking reaction; after the pre-esterification reaction, fatty acid in the raw oil is converted to the typical components of biodiesel of fatty acid methyl ester and fatty acid alkyl methyl ester, so that products directly form the biodiesel without later blending, and can be mixed with the diesel at any ratio for use.
Description
Technical field
The utility model belongs to renewable energy source domain, relates in particular to the equipment of a kind of palm dregs of fat and acidification oil refining biofuel.
Background technology
Along with beating of China energy crisis alarm bell, with the intensive prerequisite that is utilized as of the energy, fully develop the clean energies such as bioenergy, sun power, more and more become a kind of common recognition.According to scholarly forecast: new forms of energy and renewable energy source will become the frontier of the whole world and enterprise development.
China is as a developing country; be faced with the dual role that economic growth and environment increase protection; for protection of the environment and realize economic sustainable growth; change energy development and Consumption patterns; developing renewable energy source is necessary selection; therefore, renewable energy source has wide potentiality and development prospect, tankage, acidification oil, trench wet goods waste animal and vegetable oil after its main raw material is concise from Vegetable oil lipoprotein, animal grease, vegetables oil.
The palm dregs of fat and acidification oil are one of raw materials of important production of biodiesel, have formed the refining plam oil ability of daily output 20,000 tons of left and right of plam oil in China, and the palm dregs of fat and acidification oil gross annual output amount are about 600,000 tons.Plam oil saturated fatty acid content is higher, and the palm dregs of fat and acidification oil are sufficient as its source of main byproduct of plam oil physical refining, are the most cheap raw materials of production biofuel, and its physico-chemical property is in Table 1.
Because saturated fatty acid, the free fatty acid content of the palm dregs of fat and acidification oil are very high, average content is not less than 80%, therefore fusing point is higher, under normal temperature condition, solidify, therefore take the palm dregs of fat or acidification oil as raw material refining biofuel, first must solve lipid acid transition problem, generate fatty acid methyl ester, to reduce the fusing point of product.
There are two standards in country at present biofuel aspect, being respectively GB/T25199-2010 < < biofuel Blended fuel (B5) > > and GB/T20828-2007 < < diesel-fuel is in harmonious proportion with biofuel (BD100) > >, wherein the content of fatty acid alkyl methyl esters is 5% at present, and all technical of biofuel requires as table 2.
Table 1, the physico-chemical analysis characteristic of the palm dregs of fat and acidification oil
[13]
Table 2, blending biofuel (BD100) technical requirements and test method
Technology main purpose in the palm dregs of fat of carrying out at present and acidification oil refining biofuel is to produce fatty acid methyl ester and fatty acid alkyl methyl esters, and then uses fatty acid methyl ester and fatty acid alkyl methyl esters and derv fuel oil to blend, and produces blending biofuel.The content of this harmonic biodiesel fatty acid alkyl methyl esters is lower, and the content of the fatty acid alkyl methyl esters of international standard biofuel is all not less than 15%, therefore must use a kind of brand-new technique means, direct production meets international standard and country is about to the B15 of appearance and the biofuel of B20 standard, be that fatty acid alkyl methyl esters content is not less than 15%, and the biofuel of this B15 of meeting and B20 standard can be mixed use with arbitrary proportion with existing GB diesel oil.
Carry out at present take the palm dregs of fat and acidification oil as raw material, take that to produce the production of biodiesel technology production time that fatty acid methyl ester is object long, the small molecules chain that the long carbon molecular rupture in lipid acid need to be become be less than 18 carbon just can carry out following process, need to use excessive methyl alcohol and concentrated acid catalyzer, later separation, purification difficulty are larger, therefore need to create a kind of new pattern, can complete fast the conversion process of fatty acid methyl ester and fatty acid alkyl methyl esters, and follow-up needs considered separated, purification problem, and direct production goes out finished product.
Utility model content
The purpose of this utility model is to provide the equipment of a kind of palm dregs of fat and acidification oil refining biofuel, to overcome prior art above shortcomings.
The purpose of this utility model is to be achieved through the following technical solutions:
The equipment of a kind of palm dregs of fat and acidification oil refining biofuel, comprise catalytic pyrolysis equipment, pre-ester conversion unit, rectifying device, tail gas gas fired-boiler and water treatment system, described catalytic pyrolysis equipment comprises fuel oil preheating tank, heating pyrolyze tank, catalytic pyrolysis tower, subcooler, condensation withdrawing can and heavy oil water-to-water heat exchanger, between described fuel oil preheating tank and heating pyrolyze tank, be provided with high temperature oil pump, described catalytic pyrolysis tower is located at heating pyrolyze tank top, described catalytic pyrolysis tower is connected with subcooler by pipeline, described condensation withdrawing can is located at the bottom of subcooler, described pre-ester conversion unit comprises pre-ester retort, methanol tank, sulphuric acid tank and depickling water washing tank, and described methanol tank, sulphuric acid tank and depickling water washing tank are all communicated with pre-ester retort, described rectifying device comprises rectifying preheating can, and described rectifying preheating can is communicated with depickling water washing tank, and described rectifying preheating can is connected with rectifying tower, and described rectifying tower top is provided with stainless steel foil water cooler, and described stainless steel foil water cooler bottom is provided with rectifying product storage tank.
Further, described subcooler, heavy oil water-to-water heat exchanger and pre-ester retort are all connected with tail gas gas fired-boiler.
Further, described pre-ester retort and depickling water washing tank are all communicated with water treatment system.
Further, described fuel oil preheating tank and heating pyrolyze tank are all communicated with heavy oil water-to-water heat exchanger.
The method of the palm dregs of fat and acidification oil refining biofuel, comprises the following steps:
1) the palm dregs of fat and acidification oil catalytic pyrolysis are the short chain fatty acid below 18 carbon, further comprising the steps:
1.1) by the palm dregs of fat and acidification oil preheating, be liquid;
1.2) with high temperature oil pump, the liquid palm dregs of fat and acidification oil are sent in electrothermal oven and are heated, at 200 ℃, with the interior moisture that completes, evaporate, between 220-380 ℃, evaporate oil vapour, oil vapour is transformed into short chain (18 carbon are following) lipid acid, alkene and alkane after the catalysis of catalyst for cracking pipeline; And
1.3) lipid acid of small molecules chain, alkene and alkane condensation are reclaimed;
2) short chain fatty acid esterification, further comprising the steps:
2.1) oil content condensation being reclaimed is input in pre-ester retort;
2.2) under 70-75 ℃ of condition, to the vitriol oil of inputting methyl alcohol and concentration 98% in pre-ester retort, reaction generates fatty acid methyl ester and fatty acid alkyl methyl esters, and methyl alcohol input is saturated fatty acid content 1/2, and vitriol oil add-on is 3% of saturated fatty acid total amount; And
2.3) after having reacted, by the standing half an hour of liquid in pre-ester retort, use separating funnel in liquid, containing sour water, to divide discharge, then use the remnants acid in sodium hydroxide saturated aqueous solution neutralising fluid, again after standing 15 minutes, use separating funnel that saliferous moisture is discharged, the oil content after dehydration is input in rectifying conservation tank;
3) short chain fatty acid after esterification is converted into biofuel, further comprising the steps:
3.1) oil content after dehydration is input to rectifying in rectifying tower from rectifying conservation tank, rectification temperature is 360 ℃;
3.2) after rectifying evaporation, oil gas, through the condensation of stainless steel foil water cooling heat exchanger, becomes biofuel finished product.
Further, step 1.2) catalyst for cracking in is nickel salt catalyzer, and described nickel salt catalyzer main component is single nickel salt, nickelous carbonate and nickel oxide.
Further, the preparation method of catalyst for cracking comprises the following steps:
1) by nickel salt break-up of catalyst powdered;
2) nickel salt powder is modulated into lotion;
3) by step 2) in lotion to be twisted into diameter be spheroid or the right cylinder particle between 0.5mm-4mm;
4) sinter molding under 800 ℃ of conditions by spheroid in step 3) or right cylinder particle, makes granules of catalyst.
Further, the minimum hole of described catalyst for cracking is 200-300 nanometer.
The beneficial effects of the utility model are: equipment of the present utility model passes through scission reaction, make to have contained the diesel fuel compositions such as a large amount of alkene, alkane in pre-ester reaction stock oil before, after pre-ester reaction, lipid acid in stock oil is converted into the biofuel typical compositions such as fatty acid methyl ester and fatty acid alkyl methyl esters, thereby make product directly become biofuel, and do not need the mediation in later stage to prepare, can mix with arbitrary proportion use with diesel oil.
Accompanying drawing explanation
With reference to the accompanying drawings the utility model is described in further detail below.
Fig. 1 is that the palm dregs of fat and the acidification oil described in the utility model embodiment refined the equipment schematic diagram of biofuel;
Fig. 2 is the transformation efficiency graph of a relation of methanol usage and saturated fatty acid in the catalytic pyrolysis process described in the utility model embodiment;
Fig. 3 is the transformation efficiency graph of a relation of catalyst levels and saturated fatty acid in the catalytic pyrolysis process described in the utility model embodiment;
Fig. 4 is the transformation efficiency graph of a relation of temperature of reaction and saturated fatty acid in the catalytic pyrolysis process described in the utility model embodiment;
Fig. 5 is the transformation efficiency graph of a relation of reaction times and saturated fatty acid in the catalytic pyrolysis process described in the utility model embodiment.
In figure:
1, fuel oil preheating tank; 2, heating pyrolyze tank; 3, catalytic pyrolysis tower; 4, subcooler; 5, condensation withdrawing can; 6, heavy oil water-to-water heat exchanger; 7, tail gas gas fired-boiler; 8, pre-ester retort; 9, depickling water washing tank; 10, methanol tank; 11, sulphuric acid tank; 12, rectifying preheating can; 13, rectifying tower; 14, stainless steel foil water cooler; 15, rectifying product storage tank; 16, water treatment system.
Embodiment
As shown in Figure 1, the equipment of a kind of palm dregs of fat described in the utility model embodiment and acidification oil refining biofuel, comprise catalytic pyrolysis equipment, pre-ester conversion unit, rectifying device, tail gas gas fired-boiler 7 and water treatment system 17, described catalytic pyrolysis equipment comprises fuel oil preheating tank 1, heating pyrolyze tank 2, catalytic pyrolysis tower 3, subcooler 4, condensation withdrawing can 5 and heavy oil water-to-water heat exchanger 6, between described fuel oil preheating tank 1 and heating pyrolyze tank 2, be provided with high temperature oil pump, described catalytic pyrolysis tower 3 is located at heating pyrolyze tank 2 tops, described catalytic pyrolysis tower 3 is connected with subcooler 4 by pipeline, described condensation withdrawing can 5 is located at the bottom of subcooler 4, described pre-ester conversion unit comprises pre-ester retort 8, methanol tank 10, sulphuric acid tank 11 and depickling water washing tank 9, and described methanol tank 10, sulphuric acid tank 11 and depickling water washing tank 9 are all communicated with pre-ester retort 8, described rectifying device comprises rectifying preheating can 12, described rectifying preheating can 12 is communicated with depickling water washing tank 9, described rectifying preheating can 12 is connected with rectifying tower 13, and described rectifying tower 13 tops are provided with stainless steel foil water cooler 14, and described stainless steel foil water cooler 14 bottoms are provided with rectifying product storage tank 15, described subcooler 4, heavy oil water-to-water heat exchanger 6 and pre-ester retort 8 are all connected with tail gas gas fired-boiler 7, described pre-ester retort 8 and depickling water washing tank 9 are all communicated with water treatment system 16, described fuel oil preheating tank 1 and heating pyrolyze tank 2 are all communicated with heavy oil water-to-water heat exchanger 6.
The palm dregs of fat and acidification oil become liquid through preheating, to be pumped in electrothermal oven, heat, at 200 ℃, with the interior moisture that completes, evaporate, from the oil vapour of evaporation between 220-380 ℃, after the catalysis of catalyst for cracking pipeline, be transformed into small molecules chain (below 18 carbon) lipid acid, alkene and alkane, after condensation, reclaim, complete long molecular chain lipid acid breaking-down process.In condensation removal process, produced a small amount of not inflammable gas of condensable recovery, be mainly alkane and the olefin gas below four carbon, overall proportion is about the 4-6% of the palm dregs of fat and acidification oil weight; Lipid acid, alkane, the olefin liquid total amount that condensation is reclaimed is about the 80-84% of the palm dregs of fat and acidification oil weight, and residue 10-14% composition, for evaporation raffinate, is mainly high boiling macromolecule component, can be used as industrial heavy oil.
The equation of catalytic cracking reaction is as follows:
CH
3·(CH
2)
n·COOH
cH
3·(CH
2)
1/3—1/2n·COOH + CnH
2n+CnH
2n
+2
Reaction completes under high temperature and catalyst action.In scission reaction, follow condensation reaction to occur, the hydrogen that scission reaction need to be supplementary is by producing alkene and condensation reaction is supplied with.Catalyzer is degradation failure in use, and the general out-of-service time is work 1.5 ten thousand hours, and inefficacy rear catalyst can be regenerated, the regeneration means new sintering of attaching most importance to, and catalyzer can be regenerated 5 times.
After catalytic pyrolysis, in the lubricant component that condensation is reclaimed, saturated fatty acid content is about 20-40%, the oil content that condensation is reclaimed is input in pre-ester retort, under 70-75 ℃ of condition, to the vitriol oil of inputting methyl alcohol and concentration 98% in pre-ester retort, methyl alcohol input is 1/2 of saturated fatty acid content, vitriol oil add-on is 3% of saturated fatty acid total amount, the transformation efficiency relation of methanol usage and saturated fatty acid is shown in Fig. 2, the transformation efficiency relation of catalyst levels and saturated fatty acid is shown in Fig. 3, the transformation efficiency relation of temperature of reaction and saturated fatty acid is shown in Fig. 4, the transformation efficiency relation of reaction times and saturated fatty acid is shown in Fig. 5.
Reaction equation is as follows:
RCOOH + CH
3OH
RCOOCH
3 + H
2O
This reaction total time is about 2 hours, and after having reacted, the total content of fatty acid methyl ester and fatty acid alkyl methyl esters is not less than 20%.
After having reacted, by the standing half an hour of liquid in pre-fat retort, then use separating funnel in liquid, containing sour water, to divide discharge, then use sodium hydroxide saturated aqueous solution to carry out the remnants acid in neutralising fluid, again after standing 15 minutes, use separating funnel that saliferous moisture is discharged, the oil content after dehydration is input in rectifying conservation tank, prepares rectifying.
Oil content after dehydration is input to rectifying in rectifying tower from rectifying conservation tank, and rectification temperature is 360 ℃, and after rectifying evaporation, oil gas, after the condensation of stainless steel foil water cooling heat exchanger, becomes biofuel finished product, and output is the more than 95% of rectifying total amount of liquid; Remaining component is distillation residual liquid, can be used for industrial heavy oil, and output is 3% left and right; In condensation, produce a small amount of uncondensable combustion gas, after reclaiming, for system, output is no more than 2%.
Use the object of stainless steel foil to be to increase condensation area, improve condensation efficiency.
The catalyst for cracking using is nickel salt catalyzer, and catalyzer principle is as follows:
Nickel salt catalyzer is mainly compound nickel salt, main component is single nickel salt, nickelous carbonate and nickel oxide, there is cracking reaction and condensation reaction on this nickel salt surface in saturated fatty acid vapour, the hydrogen ion that condensation reaction is deviate from adds in cracking reaction, completes the internal recycle of goods and materials.
In order to guarantee that the product after cracking can pass through catalyst channels completely, and condensation reaction resultant is tackled in heating pyrolyze tank, nickel salt catalyzer need to be made into the porous small ball that hole is 200-300 nanometer, concrete manufacture craft is as follows:
Nickel salt catalyst powder is broken into the powder (300 order left and right) of 50 microns of left and right, nickel salt powder is modulated into lotion, be twisted into again spheroid or right cylinder particle that diameter is sizes between 0.5mm-4mm, then sinter molding under 800 ℃ of conditions, make granules of catalyst, the minimum hole of catalyzer granulation is about 200-300 nanometer.
In use, after catalyst pores is reached 60% by area carbon covering, catalyst failure.After catalyst failure, catalyzer is sent in sintering oven, under oxidizing atmosphere, under 800 ℃ of conditions, sintering is 24 hours, and area carbon oxidation disappears, catalyst regeneration restore funcitons.
In all biological diesel production system, first will guarantee anoxybiotic in system, the anoxybiotic means of use are to drive the air composition in container with shielding gas such as nitrogen, argon gas; In system, carry out the airtight means of all links, prevent that oil gas from leaking or Air infitration system in.
Device systems workflow is described as follows:
In the incoming stock oily preheating can 1 of the raw materials for production palm dregs of fat and acidification oil, keep 60 ℃ of temperature, origin of heat is in tail gas gas fired-boiler 7, the palm dregs of fat in fuel oil preheating tank 1 and acidification oil are input in heating pyrolyze tank 2 with high temperature oil pump, add-on is 80% of heating pyrolyze tank 2 capacity, when stock oil is evaporated to residue 50% time, continuation adds new stock oil with pump in system, add mode for spraying into, in order to guarantee the continuity of system works, adopt periodic spray regime, within every 1 minute, spray once, one time injecting time is 2-3 seconds, catalytic pyrolysis tower 3 is placed on the top of heating pyrolyze tank 2, the oil vapour of evaporation directly enters in catalyst channels, complete cracking and the condensation reaction of oil gas, the lysate of scission reaction enters subsequent technique by catalytic pyrolysis tower 3, and condensation reaction products falls back in heating pyrolyze tank 2, become raffinate, 2 tons of stock oils of every every evaporation of crack tank in system, discharge raffinate 1 time, quantity discharged is 50% of raffinate amount, high temperature in keeping system, guarantees system non-stop run, oil vapour scission reaction resultant enters after subcooler 4 condensations by pipeline after catalytic pyrolysis tower 3, enter in condensation withdrawing can 5, there is the uncondensable inflammable gas of part to discharge through the top of subcooler 4, after directly reclaiming, enter in tail gas gas fired-boiler 7, produce hot water for preheating in system and pre-ester reaction heating, the oil content that condensation is collected is sent into and in pre-ester retort 9, is carried out pre-ester reaction, in methanol tank 11 and 12 pre-ester retort 9 of sulphuric acid tank, quantitatively input methyl alcohol and acid catalyst, methyl alcohol add-on is 50% of saturated fatty acid total amount, concentrated sulfuric acid catalyst add-on is 3% of saturated fatty acid total amount, starting the whipping appts that carries in pre-ester retort 9 stirs with the rotating speed of 60 turn/min, reaction design temperature is 70 ℃, reaction times is 1 hour, after having reacted, reaction liquid is transferred in depickling water washing tank 10, first after standing half an hour, use separating funnel to divide discharge by the sour water that contains that is deposited in bottom, and then use aqueous sodium hydroxide solution titration to neutralize, neutralize the clear water that adds 10% in backward liquid, in neutralization and water washing process, use whipping appts to stir according to the rotating speed of 60 turn/min, after stirring 6min in washing, stop, standing half an hour again, then moisture is used separatory to leak platform discharge, the water of twice discharge all enters unified processing in Sewage treatment systems, after washing and having dewatered, the reacted oil content of pre-ester is transported in rectifying preheating can 13, with 60 ℃ of temperature, maintain constant temperature, then be input to and in rectifying tower 14, carry out rectifying, the processed oil steam producing after rectifying enters in rectifying product storage tank 16 after stainless steel foil water cooler 15 is cooling, produces finished product, in rectifying, will produce a small amount of raffinate, in rectifying, get rid of at any time, as industrial heavy oil, mix use with the raffinate producing above.
During residual liquid discharge, in order to reclaim the heat carrying in raffinate, system is provided with a heavy oil water-to-water heat exchanger 6, first residual liquid discharge enters heavy oil water-to-water heat exchanger 6 out time, after release of heat, flow in heavy oil hold-up vessel, and the hot water obtaining directly enters use in tail gas gas fired-boiler 7, to improve water rate of heating, reduce the energy consumption of heating water.
The utility model is not limited to above-mentioned preferred forms; anyone can draw other various forms of products under enlightenment of the present utility model; no matter but do any variation in its shape or structure; every have identical with a application or akin technical scheme, within all dropping on protection domain of the present utility model.
Claims (4)
1. the equipment of the palm dregs of fat and acidification oil refining biofuel, it is characterized in that: comprise catalytic pyrolysis equipment, pre-ester conversion unit, rectifying device, tail gas gas fired-boiler (7) and water treatment system (17), described catalytic pyrolysis equipment comprises fuel oil preheating tank (1), heating pyrolyze tank (2), catalytic pyrolysis tower (3), subcooler (4), condensation withdrawing can (5) and heavy oil water-to-water heat exchanger (6), between described fuel oil preheating tank (1) and heating pyrolyze tank (2), be provided with high temperature oil pump, described catalytic pyrolysis tower (3) is located at heating pyrolyze tank (2) top, described catalytic pyrolysis tower (3) is connected with subcooler (4) by pipeline, described condensation withdrawing can (5) is located at the bottom of subcooler (4), described pre-ester conversion unit comprises pre-ester retort (8), methanol tank (10), sulphuric acid tank (11) and depickling water washing tank (9), and described methanol tank (10), sulphuric acid tank (11) and depickling water washing tank (9) are all communicated with pre-ester retort (8), described rectifying device comprises rectifying preheating can (12), described rectifying preheating can (12) is communicated with depickling water washing tank (9), described rectifying preheating can (12) is connected with rectifying tower (13), described rectifying tower (13) top is provided with stainless steel foil water cooler (14), and described stainless steel foil water cooler (14) bottom is provided with rectifying product storage tank (15).
2. the equipment of the palm dregs of fat according to claim 1 and acidification oil refining biofuel, is characterized in that: described subcooler (4), heavy oil water-to-water heat exchanger (6) and pre-ester retort (8) are all connected with tail gas gas fired-boiler (7).
3. the equipment of the palm dregs of fat according to claim 2 and acidification oil refining biofuel, is characterized in that: described pre-ester retort (8) and depickling water washing tank (9) are all communicated with water treatment system (16).
4. the equipment of the palm dregs of fat according to claim 3 and acidification oil refining biofuel, is characterized in that: described fuel oil preheating tank (1) and heating pyrolyze tank (2) are all communicated with heavy oil water-to-water heat exchanger (6).
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|---|---|---|---|
| CN201320655834.7U CN203530281U (en) | 2013-10-22 | 2013-10-22 | Device for refining biodiesel by palm oil residues and acid oil |
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|---|---|---|---|
| CN201320655834.7U CN203530281U (en) | 2013-10-22 | 2013-10-22 | Device for refining biodiesel by palm oil residues and acid oil |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103540414A (en) * | 2013-10-22 | 2014-01-29 | 惠州市神州创宇低碳技术发展有限公司 | Method and equipment for refining biodiesel through palm oil residue and acidic oil |
-
2013
- 2013-10-22 CN CN201320655834.7U patent/CN203530281U/en not_active Withdrawn - After Issue
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103540414A (en) * | 2013-10-22 | 2014-01-29 | 惠州市神州创宇低碳技术发展有限公司 | Method and equipment for refining biodiesel through palm oil residue and acidic oil |
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Granted publication date: 20140409 Effective date of abandoning: 20160106 |
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