FR2519019A1 - Fluid fuel prepd. from fine particles of biomass - or of its processed prods. by mixing with oil and viscous aq. soln. contg. surfactant - Google Patents

Abstract

A colloidal fluid fuel compsn. comprises (i) ligneous or herbaceous biomass, the by-prods. of its chemical processing or the prods. of carbonising any of these, each in the form of 104 micron or smaller particles, (ii) about an equal wt. of fuel oil, kerosene or used oil, and (iii) a mixt. of a surfactant and a very viscous aq. soln. The componentnts are well mixed to a fluid of viscosity 1,500-9,000 cP. Used as a designable clean fuel, esp. for use near the point of prodn. of the biomass. Addn. of component (ii) compensates for the low density and low calorific value of (i).

Description

 The present invention relates to a composite fluid fuel comprising woody biomass, herbaceous biomass, their carbonization products and oils, and a process for the production of this fuel.

 In today's modern society, fuels for household use are most often gaseous or liquid fuels with a calorific value of more than 27,205,750 joules, while industrial boilers and agricultural equipment also use liquid fuels which are easy to handle, of a high calorific value, such as fuel oil and kerosene. The recent oil shortage, however, has caused its price to rise sharply and rapidly, raising strong voices regarding the need for other fuels.

 Under these conditions, woody or herbaceous biomass has regained its popularity as a direct fuel, with the resulting production of firewood, Ogalite, codex, charcoal, etc.

 Demand for biomass in Japan, however, is very low compared to total energy demands.

 The woody and herbaceous biomass in its initial state is an amorphous solid matter containing water and its chemical structure includes oxygen atoms. The reported methods for liquefying biomass use the addition of hydrogen at elevated temperature and pressure in the presence of a special catalyst. These methods, however, require further studies to reduce the cost. One of the drawbacks of woody and herbaceous biomass is its absolute low calorific value, namely 4,500 kcal / kg when it contains about 30 t of water, resulting in a narrow range of uses as fuel. bulk density which has a great influence on the transport of fuels, that of biomass is very low, namely 0.1 or less, while those of petroleum and coal are approximately 0.8 and 0.7, respectively . Other main disadvantages of biomass include its low heat of combustion and its high transport cost. Thus, woody and herbaceous biomass has many disadvantages compared to petroleum-based fuels.

 The present invention is a result of one of the efforts to overcome these drawbacks and to find new biomass fuels meeting the requirements for the current national lifestyle, attaching particular importance to the local use of energy. In detail, the present invention relates to the transformation of woody and herbaceous biomass obtainable locally into composite fuels.

 Recently, the term "biomass" is often used in fields related to energy. Biomass can be defined here as living matter which is collected in mass and used as a source of energy, food and industrial materials, or as products of biological activities. It can be broadly divided into terrestrial and marine biomass.

The terrestrial biomass can also be divided into (l) woody biomass (2) herbaceous biomass (3) farinaceous biomass (4) saccharide biomass (5) hydrocarbon biomass (6) waste biomass
A journal called "Wood Industry" contains an article reviewing composite fluid fuels derived from the above categories of biomass (pages 10-16, May 1981 issue, published by The Wood Technological-Association of Japan).

 The present invention especially relates to composite fluid fuels based on woody and / or herbaceous biomass and to their production process. In this process, the woody biomass, the herbaceous biomass, their industrial by-products and / or their carbonization products are pulverized to a particle size of less than 100 mesh (152 microns) preferably less than 150 mesh (104 microns) and then mixed with an equal or lesser weight of fuel oil or kerosene. To the mixture is added 2% or less (by weight, based on the mixture) of a very viscous dispersant solution prepared by the addition of a solution of 25% or less of a neutral surfactant of the soluble type in water to a very viscous aqueous solution of a high molecular weight substance. The pH of the resulting fluid is then adjusted to an approximately neutral level, its water content below the fiber saturation point of the contained biomass and its viscosity at a value between 1500 and 9000 cPo.

 The present invention aims to provide fuels called "Designable Clean Fuels", whose viscosity, degree of gelation, calorific value, etc., can be adjusted by adjusting the proportions of woody biomass, herbaceous biomass and oil, and / or the amount of water.

 The fluid fuels associated with the present invention can burn in an atmosphere of poor mixed air, since their air / fuel ratio is smaller than that of coal due to the fact that their dual-constituent constituent contains adsorbed water and atoms of in its molecule. The exhaust gas eri7is by their combustion also contains lower concentrations of harmful substances. In addition, it is useful to reduce the emission of harmful gases due to an excess of water contained in the fluid fuel. The woody or herbaceous biomass to be used for this invention is for example forest waste wood, waste wood exploitation of timber, agricultural by-products (rice straw, rice husks, etc.), waste from factories processing agricultural or forestry products, peat, fragments of oil shale and fine particles of oil shale for oil recovery.

 By-products from chemical plants using woody or herbaceous biomass as starting material include by-products of wood saccharification plants, by-products of SCP (single cell protein), by-products of fermentation processes producing alcohol or methane and residual by-products of alcohol production from cassava or sweet sorghum.

The oils used in the present invention include recovered used oils as well as fuel oil
A or B and kerosene.

 The dispersants for the present invention are viscous substances of high molecular weight, such as sodium alginate, CMC, starch glue, molasses by-products, sodium polyacrylate, polyethylene glycol. In the present invention, 25% or less of a surfactant is added to a highly viscous aqueous solution of the dispersant mentioned above. The use of a surfactant only results in poor dispersibility and poor stability of the biomass component, but the use of a dispersion of the surfactant in a very viscous substance satisfactorily improves the properties thereof. above and allows the use of inexpensive surfactants, eliminating the need to use specially prepared surfactants.

 The surfactants used in the present invention are of the neutral type soluble in water.

 Surfactants are broadly classified as anionic, cationic, nonionic and the like. The present invention mainly uses anionic or nonionic surfactants because of their availability and their low price which are important factors for the marketing of fluid fuels. In detail, the anionic surfactants having a group -SO 3 - or group OS 3 are suitable for the present invention, including those of the alkyl benzene sulfonate type, of the petroleum sulfonate type, of the fatty acid alpha-sulfo ester type and of the olefin sulfonate type. The nonionic surfactants which can be used for the present invention are compounds of high molecular weight composed of 1,3-butane diol, triethylene glycol, octyl phenol, etc., as a group. hydrophobic, and butylene oxide, propylene oxide, ethylene oxide, etc., which are introduced by an addition reaction.

 The highly viscous substances used in the present invention include naturally occurring substances, such as aqueous viscous solutions of sodium alginate, CMC (carboxymethyl cellulose), HEC (hydroxyethyl cellulose), starch glue, molasses, and ground algae powders, as well as synthetic substances such as aqueous solutions of sodium polyacrylate, polyvinyl alcohol and polyethylene glycol. These substances can be used individually or in combination to stabilize composite fluid fuels and adjust their viscosity in the range of 1,500-9,000 cPo.

 These substances added to the fuels are high molecular weight electrolytes and their aqueous solutions have a structural viscosity which depends on the speed gradient of the mixing operation, i.e. these solutions are very viscous in the stationary phase, but that their fluidity increases as a result of a reduction in viscosity when shaken. Structural viscosity is one of the important properties for the very viscous substances used in the present invention.

 The fluid fuels according to the present invention contain water which is adsorbed on their woody and / or herbaceous biomass constituent (approximately 30% relative to the total weight of the fuel). For example, 1 kg of fuel including biomass and oil in a 1: 1 ratio contains a maximum of 150 g of water. The combustibility and combustion efficiency of the fuel have been shown to be good within these moisture content limits.

 Combinations of the highly viscous substances indicated above, surfactants and water make it possible to prepare stable fuels. In addition, their composition proportions regulate the calorific value and the viscosity of fuels between wide limits.

 The present invention uses a mortar type mixer to give a colloidal mixture. Its appropriate speed of rotation is not great, but is between 1000 and 3000 revolutions per second (tps). The use of a wet mixing technique is preferable for charred biomass. The following procedures are used for the mixing operation: After placing the woody and / or herbaceous biomass in the mixer and then the specified oil, the mixing operation is started. A few seconds later, the dispersant solution prepared according to the specified requirements is gradually added. After the addition of the dispersant is finished, the speed of rotation of the mixer is adjusted between 1,000 and 3,000 rpm. The colloidal fluid fuel is obtained 20 to 30 seconds later.

 Fluid fuels according to the present invention have the following advantages: their combustion can be easily regulated due to their fluid state; they are suitable as fuels for general use because their calorific value is much higher than that of woody or herbaceous biomass alone; and they are inexpensive because they are produced using woody biomass, herbaceous biomass, by-products - from processing industries using biomass as raw material, oil shale, peat, etc. .

 The invention is illustrated by the following nonlimiting examples.

Example 1
200 g of fuel oil A are added to 210 g of finely pulverized bituminous shale (containing 7% water). The whole is mixed well in a mixing tank. 5 g of sodium alginate are placed in 43.3 g of water and the mixture is mixed so as to obtain a very viscous solution, to which 4 g of a surfactant comprising a neutral mixture of a compound are added. of the n-alkyl benzene type and of a compound of the higher alcohol type. The resulting solution is further mixed so as to obtain a weakly transparent dispersant having a reduced viscosity. 52.3 g of this dispersant are gradually added to the mixture of pulverized oil shale and fuel oil in the mixer in operation. After the addition of the dispersant is complete, the speed of the mixer is brought to about 3000 rpm and maintained at this level for several seconds. As a result, a stable colloldal fuel containing 12.55% of water is obtained.

 The fuel obtained is left for two months and its viscosity is measured. There is little difference between the measured value (2,600 cPo) and that obtained just after preparation (2,710 cPo).

 Table 1 shows the quantities of materials used, the calorific value of the fuel obtained, etc.

Table 1
Weight Composition Volume Content Power Power (g) by weight in calorific calorific (cm3) (%) calculated volume (l) me @ uré
Joules / kg) Joules / kg)
Shale oil Quantity 210 used sprayed 42.24 130.2 0.29
Dry weight (14.7 = 7%) absolute 195.3
Fuel oil 200 43.26 250.0 0.56
Dispersant (being free of water) 9 1.95 9.0 0.02 28,406,988 28,896,692
Total fuel water content 58 12.55 58.0 0.13
Total 462.3 100 447.2 1.0
Content
Constituents) Surfactant 4 7.6) Sodium Alginate substances 5 9.8 dissolved) of the dispersant) Water 43.3 82.8) Persistent
Total 52.3 17.2% (1) Calculated from the proportions of composition (calorific values of oil and pulverized oil shale taken as 46,459,050 and 19,671,850 Joules / kg, respectively)
Example 2
A residual material obtained as a by-product of the process for the preparation of alcohol from sugar cane is air dried. The air-dried material contains 2.4% water. 250 g of kerosene (kerosene) are added to 205 g of the dried cane residual material.

The whole is mixed and sprayed with a continuous mixer set at high speed. Furthermore, 4 g of CMC are dissolved in 55 g of water and the resulting CMC solution is stirred well. To this solution is added 3 g of a surfactant comprising a compound of the fatty type (nonionic) and a compound of the higher alcohol type (anionic) so as to obtain a very viscous dispersant.

This dispersant solution is well stirred.

 62 g of the dispersant are gradually added to the above sugar cane waste in the mixer in operation. After the addition is complete, the speed of the mixer is brought to 2600 rpm and maintained at this level for a few minutes. As a result, a stable colloidal fuel containing 11.61% water is obtained.

Its viscosity is 3400 cPo and remains stable for 1.5 months.

 Table 2 shows the quantities of materials used, the calorific value of the fuel obtained, etc.

Table 2
Weight Composition Volume Content Power Power (g) by weight in calorific calorific (cm3) (%) calculated volume (l) measured
Joules / kg) Joules / kg)
Cane waste Quantity 205 sugar from a used 38.68 133.3 0.26 pro- process Weight (S = 2.4%) dry alcohol production 200 absolute
Kerosene 250 48.36 312.5 0.61
Dispersant (state example of water - 7 1.35 7.0 0.01 28,540,924 28,879,950
Total fuel water content 60 11.61 60.0 0.12
Total 517 100 512.8 1.0
Constituents) Surfactant agent 3 4.8 Content of) CMC substances 4 6.5) dissolved in the dispersant) Water 55 88.7 dispersant)
Total 62 11.3% (1) Calculated according to the proportions of composition ((calorific value of oil and sugar cane waste taken as being 44,784,850 and 17,788,375 Joules / kg, respectively)
Example 3
200 g of fuel oil A are added to 210 g of pulverized peat having a water content of 10%. The peat with the added oil is mixed in a continuous mixer at a high mixing speed, giving insolubilized fine powders of peat.

 Furthermore, 4 g of starch glue is dissolved in 56 g of water and the resulting solution is well stirred. To this viscous aqueous solution is added 3 g of a surfactant comprising a fatty-type surfactant, a synthetic alcohol (C11-C15) and 3-EO (ethylene oxide) sodium sulfonate so as to obtain a very uniform viscous dispersant.

 63 g of this dispersant are gradually added to the above peat powders in the mixer in operation. After the end of the addition, the speed of the mixer is brought to 2,500 rpm and maintained at this level for a few seconds. As a result, a stable colloidal fuel containing 16.28% water is obtained. Its viscosity is 5,200 cPo and remains the same for one month.

 Table 3 shows the quantities of materials used, the calorific value of the fuel obtained, etc.

Table 3
Weight Composition Volume Content Power Power (g) by weight in calorific calorific (cm3) (%) calculated volume (l) measured
Joules / kg) Joules / kg)
Quantity used 210 39.96 126 0.27
Peat
Total dry weight (21 = 10%) 189
Fuel oil 200 42.28 250 0.54
Dispersant (water-free state) 7 1.48 7 0.02 27,084,370 27,456,880
Total fuel water content 77 16.28 77 0.17
Total 473 100 460 1.0
Constituents) Surfactant 3 4.8 Content of) starch glue substances 4 6.3) dissolved in the dispersant) Water 56 88.9 dispersant) 11.1%
Total 63 (1) Calculated from the proportions of the compositions (calorific values of oil and peat taken as 46,459,050 and 18,625,475 Joules / kg, respectively)
Example 4
Residual material from wood saccharification plants is dried so that its water content is reduced to about 7%. 200 g of fuel oil are added
Has 230 g of fine powders of the dried residual material.

The whole is mixed and insolubilized in a continuous mixer controlled at a high mixing speed (the insolubilized materials separate from the oil when the mixture is allowed to stand).

 Furthermore, 6 g of molasses are dissolved in 48 g of water and the resulting solution is stirred well. To this solution, 3 g of a mixture of surfactants comprising phenoxy ethanol, sodium sulfonate and a fatty-type surfactant are added to obtain a dispersant. This dispersant solution is well stirred so as to obtain a uniformly mixed solution.

 57 g of this uniformly mixed dispersant solution (content of dissolved substance 15.80%) are gradually added to the above insolubilized fluid in the mixer in operation. The addition is carried out by dropping the dispersant drop by drop onto the central part of the mixing tank. After the end of the addition, the speed of the mixer is brought to 2300 rpm and maintained at this level for a few seconds.

3
As a result, 465.7 cm of colloldal fuel containing 13.16% water is obtained. Its viscosity is 5000 cPo and remains the same for 1.5 months.

 Table 4 shows the quantities of materials used, the calorific value of the fuel obtained, etc.

Table 4
Weight Composition Volume Content Power Power (g) by weight in calorific calorific (cm3) (%) calculated volume (l) measured
Joules / kg) Joules / kg)
By-product of a Quantity 230 sacchari plant used 43.92 142.6 0.30 wood fication Weight per (16.1 = 7%) absolute dry 213.9
Fuel oil 200 41.07 250.0 0.54 26,988,104 27,452,694
Dispersant (water-free state) 9 1.85 9.0 0.02
Total fuel water content 64.1 13.16 64.1 0.14
Total 487 100 465.7 1.0
Constituents) Surfactant 3 5.3 Content in) Molasses substances 5 10.5) dissolved in the dispersant) Water 48 84.2 dispersant) 15.80%
Total 57 (1) Calculated according to the proportions of composition (calorific values of the oil and by-product of the wood saccharification plant taken as being 46,459,050 and 17,997,650 Joules / kg, respectively)
Example 5
200 g of kerosene are added to 215 g of fine powders of tree bark containing approximately 6% of water. The powders with the added oil are mixed and insolubilized in a continuous mixer set at a high mixing speed (the insolubilized materials separate from the oil when the mixture is allowed to stand).

 Furthermore, 7 g of hydroxyethyl cellulose are dissolved in 47 g of water and the resulting solution is stirred well. To this cellulose solution, 3 g of a mixture of surface-active agent comprising a surface-active agent of the n-alkyl benzene type and a higher alcohol are added, so as to obtain a very viscous dispersant solution (concentration : 17.54%).

 The dispersant prepared is gradually added to the insolubilized fluid above. It is recommended to drop the dispersant drop by drop on the central portion of the insolubilized fluid in the mixer while the fluid is completely agitated. After the end of the addition, the speed of the mixer is brought to 2600 rpm and maintained at this level for a few seconds. As a result, 454.6 cm3 of a colloldal fuel containing 12.69% of water is obtained. Its viscosity is 4,800 cPo and remains unchanged after abandonment for two months.

 Table 5 shows the quantities of materials used, the calorific value of the fuel obtained, etc.

Table 5
Weight Composition Volume Content Power Power (g) by weight in calorific calorific (cm3) (%) calculated volume (l) measured
Joules / kg) Joules / kg)
Quantity used 215
Source powder 42.82 134.7 0.30
Dry weight (12.9 = 6%) absolute 202.1)
Fuel oil 200 42.37 250.0 0.55 25,426,912 25,958,471
Dispersant (water-free state) 10 2.12 10.0 0.02
Total fuel water content 59.9 12.69 59.9 0.13
Total 472 100 454.6 1.0
Constituents) Surfactant 3 5.3) Hydroxyethyl Content in) cellulose 7 12.2 dispersing substances) dissolved in) Water 47 82.5 dispersing
Total 57 17.54% (1) Calculated according to the proportions of composition (calorific powers of the oil and bark powder taken as being 44,784,850 and 17,997,650.Joules / kg respectively)
Example 6
Knot waste from a pulp mill is charred at around 550 C. 180 g of char products containing 3% water and 200 g of used oil (mixture of fuel oil, kerosene and oil for machines) are placed in a mortar type mixer and mixed for several minutes. After the mixing operation, the carbonization product is sprayed to obtain a fluid in very fine particles which is insolubilized and is not miscible with the oil.

 Furthermore, 3 g of CMC and 2 g of sodium polyacrylate are dissolved in 55 g of water and the resulting solution is stirred well to obtain a very viscous fluid.

To this fluid, 3 g of a mixture of surfactants are added comprising an agent of alpha-olefin type (nonionic), one of higher alcohol type (anionic), another of higher alcohol type (nonionic) and / e bold type (non-ionic). This dispersant solution is well stirred.

63 g of the dispersant solution (concentration: 12.70%) are gradually added to the insolubilized fluid above in the mixer. It is recommended / drop the solution drop by drop on the center of rotation of the pestle. After the addition is complete, the fluid is stirred for several minutes. As a result, we
3 'obtains 434.8 cm of uniform colloldal fluid. Its viscosity is 4,600 cPo and remains stable after abandonment for two months.

 Table 6 shows the quantities of materials used, the calorific value of the fuel obtained, etc.

Table 6
Weight Composition Volume Content Power Power (g) by weight in calorific calorific (cm3) (%) calculated volume (l) measured
Joules / kg Joules / kg)
Carbohydrate product - Quantity 180 nization of waste used 39.41 116.4 0.27 knots of Weight (5.4 = 3%) dry pulp mill 174.6 absolute
Used oil (mixture) 200 45.15 250.0 0.57 31,152,676 31,608,896
Dispersant (water-free state) 8 1.81 8.0 0.02
Total fuel water content 60.4 13.63 60.4 0.14
Total 443 100 434.8 1.0
Constituents) Surfactant 3 4.76 Content of) CMC substances + polyacrylate) dissolved in sodium 5 7.94 dispersant) dispersant) Water 55 87.30) 12.70%
Total 63 (1) Claculated according to the proportions of composition (calorific powers of the oil and the carbonization product taken as being 42,692,100 and 30,135,600 Joules / kg, respectively)
Example 7
Large quantities of residual by-products are offloaded from alcohol-producing factories using sweet sorghum as their raw material. 200 g of kerosene are added to 250 g of the by-product (residual waste) containing 15% water. The by-product and the added kerosene are mixed and sprayed in a continuous mixer, giving an insolubilized fluid which is immiscible with oil.

 Furthermore, 6 g of polyethylene glycol are dissolved in 26 g of water. To this viscous solution, 3 g of a mixture of surface-active agents comprising surface-active agents of the n-alkylbenzene type and of the higher alcohol type are added. The resulting dispersant solution is mixed well.

 This very viscous dispersant (concentration: 25.71%) is gradually added to the insolubilized fluid above.

After the addition is complete, the mixing speed of the mixer is again set to 2800 rpm and held there for several seconds. As a result, a colloidal fluid containing 13.09% water is obtained.

 Its stability is excellent and its viscosity remains unchanged after abandonment for 3 months. The measured value of its viscosity is 1850 cPo.

 Table 7 shows the quantities of materials used, the calorific value of the fuel obtained, etc.

Table 7
Weight Composition Volume Content Power Power (g) by weight in calorific calorific (cm3) (%) calculated volume (l) measured
Joules / kg) Joules / kg)
Residual by-product Quantity 250 of a producing plant used 43.81 141.5 0.31 alcohol from Weight 37.5 = 15%) dry sweet sorghum 212.5 absolute
Combustible oil 200 41.24 250.0 0.54 26,079,850 26,548,626
Dispersant (water-free state) 9 1.86 9.0 0.02
Total fuel water content 63.5 13.09 63.5 0.13
Total 485 100 464.1 1.0
Constituents) Surfactant 3 8.57 Substance content) dissolved in polyethylene glycol dispersant 6 17.14) 25.71% dispersant) Water 26 74.29)
Total 35 (1) Calculated according to the proportions of composition (calorific values of the oil and the residual by-product taken as being 44,784,850 and 17,369,825 Joules / kg respectively)

Claims (2)

 1. Composite fluid fuel composition comprising the mixture of particles of 104 ss or less of woody biomass, herbaceous biomass, by-products of chemical plants using this biomass as raw material or their carbonization products with an approximately equal weight of fuel oil, kerosene and / or used oil, characterized in that it can be transformed into a colloidal fluid by the addition of a surfactant dissolved in a very viscous aqueous solution, that the content of The water of this fluid fuel is set below the fiber saturation point of the woody or herbaceous biomass contained, and that the viscosity of the fluid fuel is maintained in the range of 1,500 to 9,000 cPo.  2. Process for the production of a composite fluid fuel comprising the mixture of particles of 104 A or less of woody biomass, herbaceous biomass, by-products of chemical plants using this biomass as raw material or their carbonization products, with an approximately equal weight of fuel oil, kerosene and / or used oil to which is added 2% or less by weight, based on the mixture, of a mixed dispersant solution uniformly prepared by the addition of 25% or less of a surfactant to a highly viscous aqueous solution having a structural viscosity within a neutral range, characterized in that the pH of the resulting fluid fuel is set to a neutral range, that its water content is set to - below the fiber saturation point of the woody or herbaceous biomass contained and that its viscosity is maintained between 1,500 and 9,000 cPo.