CN101735847A - Method for producing rosin fuel oil - Google Patents

Abstract

The invention discloses a method for producing rosin fuel oil, which is prepared by the steps of preparing raw materials, preparing a rosin-containing mixture, preparing maleopimaric anhydride and preparing liquid rosin fuel oil. Concretely, the method comprises: heating rosin containing resin acids and maleic anhydride which can be converted to conjugated double bonds to 180 to 200 DEG C to perform an addition reaction of diene for 2 to 4 hours; performing separation to obtain maleopimaric anhydride serving as an epoxy resin-anhydride curing agent; heating the non-reacted rosin to 200 to 280 DEG C to perform an reaction in the presence of an active carclazyte catalyst to obtain the rosin fuel oil by catalytic pyrolysis. The rosin fuel oil produced by the method can be mixed with palm oil biodiesel or No.0 diesel and meet the requirements of national standards GB/T20828-2007 and GB252-2000 in terms of related indexes. The method produces the fuel oil and the maleopimaric anhydride, reduces the production cost of the fuel oil and improves the economic practicability of the production and use of the rosin fuel oil.

Description

Method for producing rosin fuel oil

Technical field

The present invention relates to a kind of method for preparing biomass fuel by rosin.

Background technology

Rosin is a kind of important renewable resources, and China has abundant pine forest resource, produces ten thousand tons of rosin 30-50 per year, and its deep processed product is widely used among the industry such as paint, soap, paper, printing ink, tackiness agent, electrical equipment, agricultural chemicals, spices.Along with oil crisis in the world wide increasingly sharpen and in view of the pressure of resource and environment; people begin to seek new not with the Technology of oil as the feedstock production biomass fuel one after another; once the main raw material that was once becoming the preparation biofuel as Vegetable oil lipoprotein has carried out big quantity research; CN1313568, CN1570029 disclose technology and the method for utilizing natural plant grease to prepare biofuel; yet because the natural fats and oils price generally than the high 10-20% of petrifaction diesel price, makes the industrial production biofuel have obstruction on economic feasibility.Therefore, how to improve the economic feasibility of biofuel synthesis route, become an important topic of present research.

CN1687316 discloses " preparation method of bio-diesel oil by rosin ", started unique approach of this biomass production oil fuel of rosin, for useful contribution has been made by society, but the oil fuel that this method makes also exists the production cost problem of higher, lack the price advantage that substitutes diesel oil, applying of technology and product is very not unobstructed.

Rosin is the complex mixture of various kinds of resin acid and little fat acid, neutral substance.Rosin heats under an acidic catalyst effect, and molecular scission can take place, and generates low-molecular-weight hydrocarbon polymer.Owing to contain unsaturated conjugated pair of key in the rosin acid molecular structure, can carry out the addition reaction of Diels-Alder diene with maleic anhydride and generate a kind of have many rings, high-molecular weight tribasic carboxylic acid maleopimaric anhydride simultaneously.Maleopimaric anhydride is as a kind of polyprotonic acid of polyfunctionality, have excellent biological degradability and biocompatibility, except that being directly used in aspects such as coating, tackiness agent, synthetic resins, after modifications such as esterification, alcoholysis, can develop a series of multiduty product innovations.The industrial maleated rosin that utilizes rosin and maleic acid anhydride reactant to obtain is actually the mixture that 50% above maleopimaric acid anhydride adduct peace treaty accounts for the neutral substance of 35% resinous acid that does not react and 10% at present, effectively separate, there are organic solvents such as employing ether, sherwood oil, tetracol phenixin to separate the technology report that obtains maleopimaric anhydride, but utilize problem to being removed the unreacted rosiny from not mentioned.The present invention directly carries out catalytic pyrolysis with rosin, but earlier synthetic maleopimaric anhydride, utilize the unreacted rosin after separating to prepare biomass fuel again, therefore, can be described as to a certain extent to utilize and produce maleopimaric anhydride residuum production rosin fuel oil, reduce the latter's production cost significantly, thereby improved the economic feasibility that rosin fuel oil is produced greatly.

Summary of the invention

The technical problem to be solved in the present invention is to utilize the rosin biomass material, in the preparation biomass fuel, obtains a kind of maleopimaric anhydride byproduct that has than high added value, improves the economic feasibility that rosin fuel oil is produced.

The technical scheme that addresses the above problem is: earlier rosin and MALEIC ANHYDRIDE unsaturated compound are carried out the diene addition reaction, its principal reaction formula is as follows:

Because this reaction need carry out under the excessive condition of rosin, so generally contain 50% left and right sides unreacted rosin in the post reaction mixture.Turps be rosin through the volatile oil that distillation obtains, be dissolving rosin solvent preferably.Utilize maleopimaric anhydride above-mentioned reaction mixture effectively can be separated with the different solubility of unreacted rosin in turps, isolate maleopimaric anhydride byproduct with higher using value, then unreacted rosin is carried out cracking under the effect of catalyzer, obtain liquid rosin fuel oil, reduced the production cost of rosin fuel oil.

Concrete production stage is as follows:

(1) preparation of raw material: want to buy commercially pure rosin, MALEIC ANHYDRIDE, turps and Glacial acetic acid to chemical industry shop or manufacturer, want to buy the atlapulgite that obtains by the calcium-base bentonite acidifying to bentonite ore or source mill, pH value 3～4, particle diameter is equal to or less than 0.1mm;

(2) rosin adds the preparation of resulting mixture: in reactor, add 100 weight part rosin, be heated to rosin fusing after, add 15～20 weight part MALEIC ANHYDRIDE again, carry out the diene addition reaction, continue to be warming up to 180～200 ℃, reaction 2～4h, stopped reaction obtains rosin and adds resulting mixture;

(3) producing of maleopimaric anhydride: when treating that above-mentioned rosin adds resulting mixture and is cooled to 100～120 ℃, add the turps of 300～500 weight parts as solvent, leave standstill 6～12h after stirring, centrifugation upper strata solvent is standby, gets light yellow precipitate, at every turn the turps 300-500 weight part that all renews, repeat above-mentioned static, isolating operation 3 times, carry out recrystallization with 100～150 weight part Glacial acetic acid again, get white crystal, be the high maleopimaric anhydride byproduct of purity;

(4) making of liquid rosin fuel oil: above-mentioned three separating obtained solvents merging are placed reactor, be heated to 160～180 ℃, behind the distillating recovering solvent, add 5～10 weight parts as the activity of such catalysts carclazyte, continue to be heated to 200～280 ℃, reaction 1～4h, cooling, decompress filter is removed atlapulgite, get pale brown look liquid rosin fuel oil, recording its density is 950～960kg/m3, and acidity is 6.9～8.2mgKOH/100ml, 20 ℃ of kinematic viscosities are 40～50mm2/s, condensation point is-30～-40 ℃, and cold filter clogging temperature is 10～12 ℃, and cetane value is 30～40, flash-point is 60～70 ℃, and 10% steaming excess carbon residue is 1.8～2.0%.

The invention has the beneficial effects as follows:

Providing a kind of is the new technology approach of feedstock production biomass fuel with rosin, when producing rosin fuel oil, obtain the higher maleopimaric anhydride byproduct of economic worth, thereby reduced production cost, solved the economic feasibility problem of rosin biomass fuel production technique.And it is nontoxic, pollution-free that the present invention separates solvent for use turps, can be recycled after the recovery.

Embodiment

The present invention is described in further detail below in conjunction with embodiment: will want to buy each raw material, its weight part proportioning value of gained earlier, the temperature and time of reaction is listed in the table below by 7 embodiment:

Embodiment one (the temperature and time parameter value of table embodiment 1 listed raw material and weight part proportioning value thereof, reaction in the reference):

In reactor, add 100 weight part rosin, be heated to fusing, the MALEIC ANHYDRIDE that adds 15 weight parts again, continue to be warming up to 180 ℃, reaction 2h promptly ends, get rosin and add resulting mixture, when treating that this mixture is cooled to 100 ℃, add the turps of 300 weight parts, leave standstill 6h after stirring as solvent, centrifugation upper strata solvent is standby, stay light yellow precipitate, so repeat above-mentioned operation totally 3 times, all add new turps 300 weight parts at every turn, leave standstill 6h after stirring equally, centrifugation upper strata solvent is standby, the light yellow precipitate that will stay after three dissolvings is carried out recrystallization with 100 weight part Glacial acetic acid at last, gets white crystal, is the high maleopimaric anhydride byproduct of purity.Again above-mentioned three separating obtained solvents are merged and place reactor, be heated to 160 ℃, behind the distillating recovering solvent (turps), add 5 weight parts as the activity of such catalysts carclazyte, continue to be heated to 200 ℃, reaction 4h, cooling, decompress filter is removed atlapulgite, gets pale brown look liquid rosin fuel oil

All the other embodiment 2-7, the raw material shown in the embodiment sequence of epiphase correspondence, proportioning weight part value, temperature of reaction and time conditions in the reference all can make this rosin fuel oil with embodiment 1 same procedure.Respectively there are some difference the proportioning raw materials value of seven embodiment and temperature of reaction and time, this can determine to react whether fully with speed of response etc., the turpentine oil content dissolves several times with separating also to be taken all factors into consideration and decides from improving percentage extraction and work efficiency, therefore also can divide secondary or four addings.Among seven embodiment, preferred with embodiment 2,4.Every embodiment all finishes under the condition of normal pressure of reactor.

This rosin fuel oil is pale brown look liquid state, after measured, its density 950～960kg/m3, acidity 6.9～8.2mgKOH/100ml, 20 ℃ of kinematic viscosity 40～50mm2/s, condensation point-30～-40 ℃, 10～12 ℃ of cold filter clogging temperatures, cetane value 30～40,60～70 ℃ of flash-points, 10% steams excess carbon residue 1.8～2.0%.

Below this rosin fuel oil is described below with the plam oil biofuel with the index of correlation of No. 0 composite back of diesel oil gained and the contrast situation tabulation of national standard requirement:

Rosin fuel oil physical and chemical parameter with the preferred embodiment 2 that records is that example is introduced below, the density 958kg/m3 of this oil fuel, acidity 7.5mgKOH/100ml, 20 ℃ of kinematic viscosity 47.6mm2/s, condensation point-30 ℃, 11 ℃ of cold filter clogging temperatures, cetane value 30.4,63 ℃ of flash-points, 10% steams excess carbon residue 1.9%.

With this oil fuel in 1% ratio be added into the brown tung oil biofuel carry out composite after, acidity is that 0.12mgKOH/100ml, 40 ℃ of kinematic viscosities are that 4.3mm2/s, condensation point are that 12 ℃, cold filter clogging temperature are that 13 ℃, flash-point are that 161 ℃, cetane value are that 57 biofuel, 90% recovered temperature are 335 ℃ after measured, and this oil meets China GB/T20828-2007 " diesel-fuel blending with biofuel (BD100) " standard-required.

With this oil fuel in 1% ratio be added into No. 0 diesel oil carry out composite after, after measured 10% steam the excess carbon residue be 0.1%, 40 ℃ of kinematic viscosity be 5.3mm2/s, condensation point for-5 ℃, cold filter clogging temperature be 1 ℃, flash-point is that 72 ℃, cetane value are 51 B1 biofuel, and this oil meets the requirement of China GB252-2000 " solar oil " national standard.

Above-mentioned two kinds of composite oil detect through Nanjing Quality Supervision and Examination Institute, and its overall target is as follows:

1% rosin fuel oil and plam oil are composite

Interventions Requested	Standard value	Measured value	Judge
				Acid number, mgKOH/g	??≤0.80	??0.12	Qualified
10% steams excess carbon residue, %	??≤0.30	??0.04	Qualified
				Kinematic viscosity (40 ℃), mm 2/s	??1.9～6.0	??4.3	Qualified
Condensation point, ℃	??---	??12	Qualified
				Cold filter clogging temperature, ℃	Report	??13	Qualified
Flash-point (remaining silent), ℃	??≥130	??161	Qualified
				Cetane value	??≥49	??57	Qualified
90% recovered temperature, ℃	??≤360	??335	Qualified

1% rosin fuel oil and No. 0 diesel oil are composite

If this oil fuel is added into the plam oil biofuel in 40% ratio, record 20 ℃ of kinematic viscosities and be 9.17mm2/s, condensation point and be 3 ℃, cold filter clogging temperature and be 11.5 ℃ biofuel, 20 ℃ of kinematic viscosities of plam oil biofuel are that 6.518mm2/s, condensation point are that 12.5 ℃, cold filter clogging temperature are 11 ℃.This oil fuel greatly reduces the condensation point of plam oil biofuel, has improved the cryogenic freezing of plam oil biofuel.

Claims (1)

1. the preparation method of a rosin fuel oil is characterized in that carrying out as follows:

(1) preparation of raw material: want to buy commercially pure rosin, MALEIC ANHYDRIDE, turps and Glacial acetic acid to chemical industry shop or manufacturer, want to buy the atlapulgite that obtains by the calcium-base bentonite acidifying to bentonite ore or source mill, pH value 3～4, particle diameter is equal to or less than 0.1mm;

(2) rosin adds the preparation of resulting mixture: in reactor, add 100 weight part rosin, be heated to rosin fusing after, add 15～20 weight part MALEIC ANHYDRIDE again, carry out the diene addition reaction, continue to be warming up to 180～200 ℃, reaction 2～4h, stopped reaction obtains rosin and adds resulting mixture;

(3) producing of maleopimaric anhydride: when treating that above-mentioned rosin adds resulting mixture and is cooled to 100～120 ℃, add the turps of 300～500 weight parts as solvent, leave standstill 6～12h after stirring, centrifugation upper strata solvent is standby, gets light yellow precipitate, at every turn the turps 300-500 weight part that all renews, repeat above-mentioned static, isolating operation 3 times, carry out recrystallization with 100～150 weight part Glacial acetic acid again, get white crystal, be the high maleopimaric anhydride byproduct of purity;

(4) making of liquid rosin fuel oil: above-mentioned three separating obtained solvents merging are placed reactor, be heated to 160～180 ℃, behind the distillating recovering solvent, add 5～10 weight parts as the activity of such catalysts carclazyte, continue to be heated to 200～280 ℃, reaction 1～4h, cooling, decompress filter is removed atlapulgite, get pale brown look liquid rosin fuel oil, recording its density is 950～960kg/m3, and acidity is 6.9～8.2mgKOH/100ml, 20 ℃ of kinematic viscosities are 40～50mm2/s, condensation point is-30～-40 ℃, and cold filter clogging temperature is 10～12 ℃, and cetane value is 30～40, flash-point is 60～70 ℃, and 10% steaming excess carbon residue is 1.8～2.0%.