FI116902B - Method and apparatus for improving the quality of the pyrolysis liquid - Google Patents

Description

11

METHOD AND APPARATUS FOR PYROLYSIC LIQUID PA1

The invention relates to a process as defined in the preamble of claim 5 and to a device as defined in the preamble of claim 11 for preparing a lysis liquid such that bior and / or such volatile substances are rapidly converted into the organic substance. 10 pyrolysis vapors which are condensed to pyrolysis.

Pyrolysis liquid, i.e. pyrolysis oil is made by dry distillation pyrolysis techniques emit volatile chemical compounds inside! 15 of biomass or similar organic a: such as wood, bark, paper, rye, vista, burning stone, peat or the like; When using a slow heating rate, pyrolysis, e.g. wood tar, typically 20 to 30% by weight is obtained. The pyrolysis fluid reduces the biomass delay time from 10 to 60 hours to 0.1 to 100 seconds. Fast speed: \ v methods of pyrolysis and chemicals v; : **: There are several known things to do.

At present, there are no known processes for the preparation of lysis fluid for incineration, i. g age production, industrial scale, preir • · * or sawdust. Usually, pyrolysis is carried out by separating the desired chemicals and the remainder p <* · · 30 for disposal. Eg Ensyn Inc., USA, made * * a * - * * nai 1 i cfidhi mm Cha rwrv + π 1 \ r \ rc i AI -ΐ / -s e ^ a ö f- λ f- 11 2

Further, the pyrolysis fluid may be subjected to various chemical processes, e.g., fractionation, e.g., for use as a building board material to replace other raw materials; 5 resins.

Pyrolysis fluid contains several hundreds of 3 compounds that affect product performance, such as shelf life, and particularly behaved in pre-heaters and nozzles for boilers, engines and gas. When the chemicals are separated from the lysing liquid, its properties are essentially reminiscent and no longer correspond to those of the lime produced from organic matter like biomass. Frequently, water and / or solvent is added to the pyrolysis fluid 15, whereby water and soluble chemicals can be separated into their own f.

Pyrolysis fluid is not stable under storage conditions. Its viscosity doubles when stored under acidic conditions and at room temperature for one year.

* * The increase in bond is due to the presence of low molecular weight compounds, such as carbo! T * 5 of condensation reactions of acids, aldehydes or ketones, either with one another or with carbonyl compounds.

A. Oasmaan et. ai (VTT Publication 306, + ·

Physical characterization of biomass-based py ... liquids. According to the application of the standard fuel oil, the storage temperature of the pyrolysis fluid is substantially lower than room temperature, which is because of the large amount of alcohol required, which has a negative impact on the economy of the process.

On the other hand, pyrolysis fluid may type! ti during storage, your biphasic phase 5 where water and its soluble components are known to have high molecular weight compom, e.g., lignin-based components. Add alcohol, organic] or ketones or the like, or mixtures thereof, to the pyrolysis fluid, e.g., about 10% by weight, and simultaneously agitating the liquid into a single phase liquid, which is only for short term storage. Another way] the biphasic fluid problem is to prepare the pyrolysine by mixing an emulsion that remains stable at Kyi for 15 minutes to hours. To date, no methods are known for preparing a pyrolysine microemulsion with normal mineral oil, which would last for one year without distinguishing. storage time can be considered as a limit for both van stability and phase separation, pyrolysis fluid produced from biomass is competitive * in the heating oil market, for example.

From patent application FI 946062 it is known: ·; ··: that when feeding the pyrolysis liquid to the boiler: the liquid begins to stretch into the 25-pot nozzle and can * * prevent the nozzle from running smoothly. In this method, an er * * * tank is connected to the feed system, in addition to the pyrolysis fluid, a solvent, alcohol, which may be fed from time to time to · · · V · 30 to purify them from pitched oil * ·

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4 lysis fluids cannot be used eg in energy lift. Further, adding solvents to the pyrolyses and using them in the washing liquids adds to the cost.

The object of the invention is to eliminate the above-mentioned problems and to provide a new type of apparatus and apparatus for use in the preparation of pyrolysis fluid. In particular, it is an object of the present invention to provide a process for producing pyrolysis fluid of improved quality at an industrial scale without having stability problems in storage and can be used in power generation. A further object is to disclose a method which is welcome.

The process and the tea according to the invention are characterized by what is stated in the claims.

The invention is based on the process of pyrolysis liquid by rapidly converting pyrolysis vapor from biomass and / or organic material containing tap 20 volatiles into a pyrolysis liquid in a condenser «· V .: according to the synthesis of pyrolysis liquid from pyrolysis vapor / 25 water and light reactive chemical by co-evaporating and / or preventing the condensation of vapor, eg vapor and light gaseous compounds. The removal of water can ... substantially reduce the phase difference between the pyrolysis fluid and the removal of light, reactive compounds from the rwrrvl ττΐ clros 5 involved in the polymerization reactions typical of: storage conditions. These compounds can be, preferably, highly hydrophilic. are easily separable together with water lid 5 agents may alternatively be hydrophobic in any type of chemical compound.

In the preparation of pyrolysis fluid from bio, e.g., sawdust, by rapid pyrolysis at 300 at a lag time of 0.1 to 10 seconds, the oxygen content in the acid state is typically about 1 wt% and light, reactive compounds are 12 to 20 wt% of the pyrolysis fluid. The proportion of minor reaction carboxylic acids is typically 11% by weight of the pyrolysis liquid. By contrast, the light weight dense compounds and / or their aqueous mixture represent only about 15% of the energy content of the product. Thus, the water content of light and light compounds does not substantially reduce the energy content of pyrolysis.

In one embodiment of the invention, the hydrocarbons, reactive compounds, are removed by a shark * 5 **: a club condensed pyrolysis fluid to the desired cell * 5 *! within 48 hours of condensation, es in *: **: 150 ° C. During this time, the light 25 teas have no time to start or catalyze my dust • i; · ϊ ·. mis reaction in pyrolysis fluid.

In one embodiment, water and light • * * Close chemical compounds is removed to a eM t in connection with the condensation. In one embodiment, • * * 30 from the digester is condensed and fractionated in step 6 to remove hot pyrolysis fluid from reactive small molecules, whereby the water content of the lysis fluid is adjusted to a desired level below 5, -% by weight of pyrolysis liquid, less than 20% by weight. As the water content of the pyrolysis fluid rises above 30-32 wt.%, The risk of phase separation substantially.

In one embodiment of the invention, the lysis vapor and / or liquid is removed from the carbon formed in the ring, e.g., coke, and solids in connection with the pyrolyser and condenser v, and / or by means of a condenser j, e.g., a separator or filter. Removal of solid 15 can prevent or retard the polymerization reactions of the chemical compounds, since the agent and / or the ages attached thereto have been found to catalyze the chemical reactions of their particles, such as polymerization, thereby reducing the yield and quality of the pyrolysis fluid, e.g.

As time increases, the risk of phase separation during the thief increases significantly. The process according to the invention can be used to prepare a heat-filtered lysis fluid having a water content adjusted to the desired level.

In one embodiment of the invention, an organic liquid is added to the pyrolysis, e.g., meth longer alcohols (C2-CJ, keto: ether, and / or mineral based fuel oil 10 as a solvent or emulsion to adjust the desired viscosity and / or flash point In addition to fraying, other mouthpieces of the pyrolysis fluid, such as lubricity or corrosion resistance

In one embodiment of the invention, the light active chemical compounds and / or the mixture thereof removed from the lysis vapor and / or fluid are recycled to a known combustion and / or chemical recovery. The energy content of the water soluble solids can be utilized in the burn. in a boiler, e.g. to produce heat, preferably together with other fuels. This does not significantly reduce the combustion process! "" 25 ingenuity, especially if the fuel efficiency of the boiler • * ·. '·· is more than two! greater than the fuel efficiency of the pyrolyser.

water supplied to the boiler and light, reactive concentrates do not pose a problem in maintaining the temperature of boiler no. Alternatively, the light compounds may be derivatized completely or δ or alternately. Due to the improved quality, the lysing fluid does not cause clogging in normal combustion and does not require the use of solvent washing systems in boilers. If necessary, the mouth 5 can be cleaned, for example, by blowing the nozzle clean with air, steam or mineral based polish! oil at.

Thanks to the invention, the quality of high-speed pyrolysis can be improved by removing water and reactive chemical compounds. Stored to prevent the storage stable deterioration of the pyrolysis fluid, i.e. aging of whiskey due to aging, and the separation of the high water content into the aqueous and organic phases.

15 improved pyrolysis fluid can be used in power generation because it clearly has a shelf life of γ.

Further, thanks to the invention, the pyrolysis: water content can be adjusted to the desired level. 20 si ns. it is possible to adjust the water filter of the hot filtered pyrolysis fluid to a normal hot filter; to a lower level.

* / In addition, due to the invention, the chemical compounds separated from the pyrolysine »* · '· * ·' and their water are recycled / utilized, for example by incineration to produce energy in the process or by the use and recovery of chemical compounds.

The invention will now be described, by way of example only, with reference to the accompanying drawings, in which: FIG. the third embodiment and Fig. 4 shows the results, the closest stability of pyrolysis fluids as a function of storage viscosity increase over time.

Figure 1 shows a main pyrolysis device according to the invention including a lyser 1 known in the art, which lysates vapor from biomass from other organic material, e.g. sawdust 10 at a main pyrolysis temperature of 300-700 ° C, and a known pyrolysis steam condenser. differentiated sex of the distillate, or alternatively evaporator, 15 den and light reactive compounds by evaporation from the pyrolysis fluid. Alternatively, the distillate evaporator 10 is connected to 1; The condensed pyrolysis liquid is passed through condenser 2 through condenser 2. From distillate 2, distillate, or alternatively evaporation, is carried out in liquid phase for 48 hours:. condensation, e.g., 95-150 ° C; | The dehydrated pyrolysis liquid 8 and reactive compounds are removed from the 25 parts of the distiller, and the mixture of water and light compounds <• * V'i is led from the top of the distiller 10 to the burners 5 or to the chemical recovery 16. Applet: ': *; Any type of distillate, evaporator, or the like, known in the art, may be used, not described in greater detail herein.

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The apparatus embodiment of Fig. 1 includes lightweight compounds and water can be pumped from the top of the distiller 10 to the boiler using the apparatus ρυ. In a boiler, a mixture of light chemical substances in water is burned together with other po! 5 with these 6, e.g. peat, coal., Fuel oil Of course, air is also introduced into the boiler. The non-condensed gases 17 can be led from the grit 2 to either the combustion boiler 5 to the digester 1.

The apparatus of Fig. 1 further comprises a known separator 4, e.g. a cyclone, for separating coarse crystal and a filter known per se for filtering the more solid solids and carbon from the pyrolysis vapor from the lyser 1. The solid separated in 15 m 4 is fed to the furnace 5. The pyrolysis vapor is filtered, for example, at 30 to 550 ° C and in the case of a hot filter at 20 ° C. The filter 3 is disposed between the separators and the capacitor 2. The filter can be alternately placed in the condenser. In addition, the tea may include a conduit after the condenser. an in-line filter to extract 12 solids from the pyrolysis fluid.

Further, the device may include an additional: w 25 device of an organic liquid, e.g., methanol, et; i / ·· ketone or ether, or mineral based po ': T; to supply the solvent to the pyrolysis liquid] · *: *: in the form of an emulsion to adjust the desired viscosity and / or stamp sweat.

. ···. 30 In addition, the device may include a kerne, • · * h. Recovery unit for light, reactive compound removal devices <The devices shown in Figures 2 and 3 include a control device 13 connected to a Sorin 2, e.g., a product vapor recovery step, to prevent complete condensation of lysis vapor. for the fractionation. The control device 13 adjusts; the temperature of condensation to such a level that lightweight, small molecule compounds 1 do not ring and can be removed in gaseous mi 10 condenser 2. Control device 13 adjusts i stepwise fractional distillation to remove condensed pyrolysis with normal water content and light, reactive paths bottom 15 Further, the device comprises a conduit 14 on the upper part of the condenser through which condensed water and light reactive compounds as well as dissolved gases can be led out of the condenser part.

20 In the device embodiment of Figure 2, after the condenser 2, a separator, or alternatively a recovery device, is disposed adjacent the conduit 14 to separate the reactive chemical compounds 18 and the condensate tower from the gas tower. 9 by means of a combustion boiler 5 for incineration or to a combustion unit or tank 16. Unconditioned non-combustible funnels 17 are fed either to the pyrolyser 1 or to the combustion chamber 5.

... 30 In the device application of Figure 3, both condensed gases * and water and light chemical

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In the applications of Figures 1-3, the bulk of the light reactive compound, e.g., 6 to 7% by weight of the pyrolysis fluid, is removed from the pyrolysine. After dehydration, the water content of the pyrolysis liquid is 5 e.g. less than 20% by weight.

In the condenser of the waste plastic of the invention, a raised temperature, e.g. 110 ° C, can be used in the condenser, whereby the lysis liquid produced can be dehydrated, which in the process is carried out with the raw material. If desired, use the desired amount, e.g., 10-50%, of a base fuel oil as a washer fluid to obtain the desired pyrolysis fluid viscosity.

Example 1

The experiment investigated the stability and water content of various pyrolyzates. The pyrolysine 20 produced by the Kel method was compared with similar previously known lysis fluids.

; Normal or rapid pyrolysis] / mystified and / or treated pyrolysines • e *

* · '· * Was performed by A. Oasmaa et al. ai (VTT Publication 3C

25 Stability Test. In a 24 h test at 80 ° C, a storage time of approximately one year under practical storage conditions was simulated, i. oxygen at room temperature.

Figure 4 shows the results obtained with stability 30. Pyrolysis fluid poles: • «m l .. 'is the viscosity of the pyrolysis fluid • m Λ 13 r

B1) pyrolysis fluid B1 + pyrolysis fluid B1) pyrolysis liquid B1 + 10% MeOH B4) pyrolysis fluid B1 which contains water and light reactive compound C1) hardwood (birch) fast pyrolysis ! prepared pyrolysis liquid C2) pyrolysis liquid Cl containing 10% water and light reactive compound

D1) Hot Filtrated Rapid Pyrolysis Liquid The pyrolysis fluid B4 and C2 were removed: in a rotary evaporator, 80 wt.

Figure 4 shows that the viscosities of the pyrolysis liquids B4 and C2 of the present invention are not: significantly during storage. Hence . method provides a [lysis liquid having a better storage * * * * '· * and lower water content than other pyrrole; 25 roads.

• · • »« * i «• ·; *: *! Example 2 • * * • · »

Pyrolysis fluid ···, 30 dots change in pyrolysis fluid in the hand.

14 r of pyrolysis liquid from sawdust and pyrolysine from pine sawdust with 50% evaporation of water and light concentrates (MPÖ2) were compared with the corresponding concept 5 pyrolysis liquids having a flash point c d). The results are shown in Table 1.

Table 1 shows that when MeOH is added to ordinary pyrolysis fluid (MPO1), the flash point is from 95 ° C to 49 ° C. Add water-methanol mixture to the pyrolysis fluid (MPO2) produced by the invention without reducing the flash point below 56 ° C. Thus, the method of the invention provides a pyrolysis liquid having an easily adjustable point at the desired point using a suitable solvent.

Table 1; Flash point control MPO1 MPO2 MPO2 + MPO2 + 8.5% 8.5% MeOH-water ____ MeOH __ (1: 1), Water, p -% __ 17.5 9.6 8.6__13.4 \ / _pH__2.4 2.5 2.9__2.7 '- * · Viscosity 9 (50 ° C), cSt 31 123 37__37 • ·: /' i Flash point: T: te, ° C_ | 95 | 95 | 54 _56 • · * • »9 9 9 • 20 The process according to the invention is suitable in those applications for the synthesis of various pyrolysis liquids 9 9 9, especially

Claims (14)

A process for producing in liquid liquid, that from biomass and / or the like: combustible substances containing organically, pyrolysis bed is formed with rapid pyrolysis, which bed is condensed into pyrolysis liquid, characterized in that the pyrolysane and / liquid are removed from water and after pyrolysis. reactive chemical compounds by and / or by preventing the meadow cone completely to improve the stability of pyrolysis. Process according to claim 1, characterized in that water and light, reactive compounds are removed by evaporation 15 hours after the condensation. 3. A process according to claim 1, characterized in that the pyrolyzene bed is condensed fractionally stepwise so as to simultaneously prevent: water vapor density and light, reactive feed <20. 4. A method according to any of the patents; 3, characterized in that from 1 to 15 wt% of pyroly, advantageously 5-10 wt% L ν. active compounds are removed. *: ··: 2. Process according to any of claims <4, characterized in that, by «water, the water content of the pyrolysis liquid is adjusted. * ··. cad level, advantageously below 30% by weight of pyrolysis * · * more advantageously below 20% by weight, to prevent:. φ 3 0 ring. 6. A process according to any of the claims * * • · rr Jii____-i_j_ i- ______- 8. A process according to any of claims 7, characterized in that the pyrolysis bed is filtered. 9. A process according to any of Claims 5 to 8, characterized in that in pyrol 2, an organic liquid is added as a solvent emulsion to adjust a desired vi and / or flash point. 10. A process according to any one of patents 10 to 9, characterized in that they remove light from the vapor and / or liquid, the compounds and / or their water mixture in a combustion boiler and / or chemically utilize it. An apparatus for producing a liquid comprising an pyrolysis from which biomass is formed and / or from similar biodegradable substances containing organic matter; light bed by rapid pyrolysis, and a condenser (the pyrolysis bed is condensed into a pyrolysis liquid, characterized in that the device contains at least one agent (10,11,13,14,15) for remote water and light reactive chemical compounds. and / or the liquid, which is a means to prevent the pyrolysis bed from fully cone in the condenser and / or to evaporate water, take reactive chemical compounds directly from the liquid after the condensation, for improvement. ··· The stability of the light liquid • * * Device according to claim 11, k. , Characterized in that the device comprises the condenser (2) connected pipe (11), through which 9. M. 1. 1 j__> __ T__n_. _ 1 20 1 13. Device according to claim 11 e, characterized in that the evaporator, casserole or similar means (10) is arranged to evaporate water and light, reactive air within 48 hours after the condensation. Device according to claim 11, characterized in that the device comprises a connection with the condenser (2) located control device for preventing the condensation of the pyrolysis bed and for fractionation of the pyrolysis bed and connection with the condenser (2) connected to the pipe ¢ 1 - which water and light, reactive chemical fc as well as non-condensed gases are conductable from the sorbent (2). Device according to Claim 11e, characterized in that the device is placed one or one after the condenser (2), recovery device or similar means separating water and light, reactive chemicals from non-condensed gases. Apparatus according to any of the claims: - 15, characterized in that the apparatus comprises a filter (3, 12) for filtering <: V: and carbon blanks from the pyrolysis bed and / or liquid · ··· 17. Some of the patents: • -βί-16, characterized in that the apparatus includes a combustion reactor (5), where the light vapor and / or liquid are removed easily, the compounds and / or their water mixture and 30 non-condensed gases are combusted with others and from which energy is fed to the pyrolysator (1).