High carbon concentration biomass and biosolids slurry preparation using a hydro-thermal pretreatment

Abstract

Provided is a process where the biomass and bisolids are hydrothermally treated under a reductive gas. Using this process a high carbon content pumpable mixture of biomass and biosolid slurry is produced with a viscosity value of less than 1.5.

Claims

1. A process for producing a pumpable high carbon content slurry comprising: providing a mixture of water and a material selected from the group consisting of an agricultural product, wood, plant, paper and cardboard, wherein the material comprises a weight percentage between 30 wt % to 70 wt % of the mixture; mixing the mixture with a residue produced from a waste water treatment process to form a slurry mixture; and heating the slurry mixture under a non-oxidative gas to thereby produce the high carbon content slurry.

2. The process of claim 1, wherein the non-oxidative gas is selected from the group consisting of argon, helium, nitrogen, hydrogen, carbon dioxide, or gaseous hydrocarbons, or mixtures thereof.

3. The process of claim 1 in which the slurry mixture is heated to the temperature having a range of 170 to 250° C.

4. The process of claim 1, wherein the slurry mixture is heated under the non-oxidative gas at a pressure of 100 to 400 psi.

5. A process for converting biomass into a higher carbon content slurry, consisting essentially of: grinding the biomass; mixing the biomass with water to thereby form a first mixture, wherein the biomass comprises a weight percentage between 30 wt % to 70 wt % of the first mixture; mixing the first mixture with a residue produced from a waste water treatment process to form a slurry mixture; and heating the slurry mixture under a non-oxidative gas to thereby produce the high carbon content slurry.

6. The process of claim 5, wherein the biomass is selected from the group consisting of an agricultural product, wood, plant, paper and cardboard.

7. The process of claim 5, wherein the non-oxidative gas is selected from the group consisting of argon, helium, nitrogen, hydrogen, carbon dioxide, or gaseous hydrocarbons, or mixtures thereof.

8. The process of claim 5, the slurry mixture is heated under the non-oxidative gas at a pressure of 100 to 400 psi.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) For a more complete understanding of the present invention, reference is now made to the following description taken in conjunction with the accompanying drawings, in which:

(2) FIG. 1 shows a flow diagram for one embodiment of the invention regarding the mixing sequence of biomass and biosolids hydrothermal treatment

(3) FIG. 2 shows a graph representing the viscosity value of pretreated biosolids and biomass under shear rate of 102 s.sup.−1 vs. water to carbon mass ratio in resultant slurries: change of initial biosolids to biomass mass ratio and initial biomass particle size (pretreatment temperature of 240° C.).

DETAILED DESCRIPTION OF THE INVENTION

(4) A new process for a pumpable “slurry formed” biomass and bisolids mixture production has been devised. The goal of high carbon content in the pumpable biomass and biosolids slurry was achieved by hydrothermal treatment of biomass and bisolids mixtures at different mixing ratios. The mixtures were then hydrothermal treated under mild thermal condition (230° C.) and a pressure of 1500 psi. A reductive gas phase in head space of the vessel was maintained by pressurization of hydrogen, or other reductive or inert gas, before the hydrothermal treatment process. The vessel was impeller agitated inside for well mixing of mixture during hydrothermal treatment.

(5) Three mixing sequences were tested as shown in FIG. 1. It was found that the third mixing sequence, which is to mix biomass with biosolids before hydrothermal treatment, gave the best result, it offered the highest carbon content in the pumpable biomass and biosolids slurry. It offered the simplest way of one mixing step for the hydrothermal treatment. It also offered direct utilization of water from biosolids with out external source of water to make slurry.

(6) In another embodiment, water rather than biosolids can be used.

(7) In another embodiment, the biosolids used to be mixed with the biomass

(8) Biomass was grinded and was then mixed with biosolids with different biomass to biosolids ratio. The control over carbon content in the biomass and biosolids slurries was carried out by mixing biomass with biosolids with different mass ratio. The resultant slurries were tested by its rheology properties, such as viscosity values for different shear rate values. It was found with initial biomass particle sizes of less than 180 um, a slurry with carbon to water ratio of over 1:2.5, equally 22.3 wt % of carbon in the slurry, was produced with a viscosity value of less than 1.0 pa.Math.s under a shear rate of 102 s.sup.−1 (FIG. 2).

(9) Gas analysis was also carried out for the resultant exhaust gas to see how much carbon was lost through the gas phase after the hydrothermal treatment process. It was found a negligible amount of carbon present in the exhaust gas phase, no more than 1%. Most of the carbon was present in the gas phase in forms of CO.sub.2 and CO, small amount of hydrocarbon with carbon numbers from 1 through 5 was also detected in the exhaust gas.

(10) The above described high carbon content biomass and biosolid slurry produced by one embodiment can be used generally in hydrogasifiers or steam hydrogasifiers more particularly disclosed in U.S. Pat. No. 7,500,997 and U.S. application Ser. No. 11/879,266 (filed on Jul. 16, 2007), which are both hereby incorporated by reference in their entirety.

(11) The term ‘biomass” as used herein refers broadly to material which is, or is obtained from, agricultural products, wood and other plant material, and/or vegetation; paper and cardboard, or any combination thereof. The biomass at the desired weight percentage, generally from 30 to 70 wt %, is mixed with water, or diluted sewage sludge/biosolids, while at a temperature in the range of 170 to 250° C., most preferably about 200° C., under non-oxidative gas pressure of 100 to 400 psi, most preferably about 150 psi. The mixture can be placed in an autoclave at room temperature and ramped to the reaction temperature, or the vessel can be preheated to the desired temperature before being pressurized. The reaction temperature can range from 10 minutes to an hour or more.

(12) In one embodiment, the biomass that is later to be mixed with water, or biosolids, does not undergo any prior drying or evaporation procedure to remove the water present in the biomass or to concentrate the biomass.

(13) In another embodiment, the definition of biomass excludes sewage sludge or biosolids. However, ‘diluted sewage sludge/biosolids’ can serve as a source of water to be mixed and heated with the biomass under pressure in the presence of the non-oxidative gas. The term ‘diluted sewage sludge/biosolids’ means sewage sludge/biosolids material that have not been heated/dried to evaporate their water content. Such diluted sewage sludge/biosolids can contain from 70% to 97.5%, or 75% to 97.5%; 80-97.5%; 90-97.57% of water.

(14) In another embodiment, biomass can include material from landfills.

(15) In another embodiment, the biomass is not mixed with any water and then later condensed, or water evaporated, prior to being mixed with water/biosolids and heated in the disclosed process under the non-oxidative gas under pressure of 100 to 400 psi, most preferably about 150 psi.

(16) In another embodiment, the biomass material used excludes material that have been treated to anerobic and aerobic conditions.

(17) In another embodiment, the high carbon content biomass and biosolid slurry does not require being mixed with coal prior to utilizing such high carbon content biomass and biosolid slurry in a hydrogasifier or steam hydrogasifier.

(18) In one embodiment, the water content of the mixture of biomass and water/biosolids, remains about the same after heating with the non-oxidative gas under pressure of 100 to 400 psi, most preferably about 150 psi. In another embodiment, the final water content of the mixture after heating with the non-oxidative gas under pressure of 100 to 400 psi, is within 40%; or 30%, or 20%, or 10% or 5% or 1% of the original mixture water content.

(19) While any non-oxidative gas can be used, such as argon, helium, nitrogen, hydrogen, carbon dioxide, or gaseous hydrocarbons, or mixtures thereof, nitrogen is preferred because of its economic availability. Another preferred non-oxidative gas is hydrogen if available internally from the process, and which can be particularly advantageous if carried with the slurry into a hydro-gasification reactor. While it is desirable to eliminate oxidative gas, one can use a commercial grade, or less pure, of the non-oxidative gas so long as no substantial oxidation takes place.

(20) The following examples will illustrate the invention.

EXAMPLE 1

(21) Referring to FIG. 1, a non-pumpable mixture of 50% biomass, consisting of pine tree particles in water is shown before treatment. Dry pine sawdust was obtained from American Wood Fibers and the dry White Cedar from Utah. The sawdust was ground using a commercially available coffee grinder and sieved to <100 mesh (150 μm). For the wood pre-treatment, an autoclave system was set up. It consisted of an Autoclave Engineers EZE-Seal pressure vessel rated at 3,300 psi at 850° F. The wood sample and deionized water were weighed and then well mixed by hand to even water distribution in a large beaker before putting it in the vessel. The amount of wood added was adjusted for moisture content. The vessel was then weighed with contents, vacuumed and purged three times with argon, and finally pressurized to 100±1 psi. The temperature was ramped to operating temperature (210-230° C.) in about 30 minutes and then held for 30 minutes. Pressure and internal temperature were recorded using a data acquisition software. After holding for 30 minutes, application of the heat was stopped and the vessel was pulled out of the heater. The vessel was left to cool to room temperature to allow collection of head space gas and sample. Temperature and pressure were recorded before collection and then the vessel was weighed.

(22) The result is shown in FIG. 2, which is a photograph of the slurry of FIG. 1 after treatment, which was a pumpable slurry containing 50 wt. % solids in water. Analysis of the head space gas showed negligible carbon, indicating negligible carbon loss from the slurry.

EXAMPLE 2

(23) The procedure of Example 1 was followed but the vessel was preheated to >200° C. before being put in the heater. The autoclave was found to reach 230° C. in 15 minutes or less and then it was held for 30 minutes. The time needed to reach the target temperature did not have a noticeable physical impact on the resulting product

EXAMPLE 3

(24) The method of Example 1 can be carried out but in which the starting mixture is non-pumpable agricultural waste containing 60 weight percent solids. The result will be a pumpable slurry containing 60 wt. % solids in water.

EXAMPLE 4

(25) The method of Example 1 can be carried out but in which the starting mixture is vegetation containing nonpumpable 40 weight percent solids. The result will be a pumpable slurry containing 40 wt. % solids in water.

(26) The slurry of carbonaceous material resulting from the process of this invention can be fed into a hydro-gasifier reactor under conditions to generate rich producer gas. This can be fed along with steam into a steam pyrolytic reformer under conditions to generate synthesis gas, as described in Norbeck et al. U.S. patent application Ser. No. 10/503,435, referred to above. Alternatively, the resultant slurry can be heated simultaneously in the presence of both hydrogen and steam to undergo steam pyrolysis and hydro-gasification in a single step, as described in detail in Norbeck et al. U.S. patent application Ser. No. 10/911,348, referred to above.

Examples Related to Commingling Biomass and Coal Slurries

(27) Others have concluded that the rheological properties of coal-water slurries, such as shear stress and viscosity, are dependent on the type of coal, solid loading, coal particle size and size distribution, temperature, and additives [5-7]. Other studies have addressed biomass suspension and the effect of particle size on rheological properties of cellulosic biomass slurries [8]. However, biomass slurry rheological studies and its potential as a gasification feedstock when co-mingled with coal have not been reported.

(28) Provided now are novel results obtained by examining the rheological properties and pumpability of various coal-water, wood-water, and commingled wood-coal-water slurries. The major factors considered are particle size, solid loading, viscosity, and a proprietary wood pretreatment procedure for the wood for the purpose of increasing the solid water ratio. Finally, the maximum solid content of co-mingled coal-wood slurries that are pumpable was evaluated.

(29) At the time the above data was produced (for the above Examples 1-4) (as disclosed in U.S. patent application Ser. No. 11/489,299) it was not appreciated that the pumpability of our hydrogasification process would be obtained with a viscosity of less than 0.7 Pas. Given this previously undisclosed fact, and that the optimum water:carbon ratio of our process is 3:1, we set out to determine how the viscosities of our pretreated biomass slurries could be improved. The following experiments show that one method of improving pumpability of biomass slurries is to commingle biomass slurries with coal slurries.

EXAMPLE 5

(30) Preparation of Coal and Wood Particles

(31) Coal and wood particles were prepared from bituminous coal from Utah and poplar sawdust. Each material was initially ground and then pulverized in a pulverizing grinder. The pulverized particles were then sieved into three particle size ranges: 0-150 μm, 150 μm-250 μm and 250 μm-500 μm. The particles were then dried in a vacuum oven for vaporization of the moisture content at 70° C. The analysis of the solid content of the coal and wood particles after the vaporization process was determined by Thermometric Gravitation Analysis (TGA). The results of the TGA are presented in Table 1. Finally, particles were mixed with water to form numerous coal and wood slurries. The solid loading for coal-water slurries ranged from 40 wt. % to 65 wt. % by every 5% and 5 wt. % to 12.5 wt. % by every 2.5% for the wood-water slurries. Mixtures were settled overnight for complete mixing of the particles and water and were then gently stirred just before the rheological tests to avoid settlement of particles. Harsh stirring was avoided to prevent small air bubbles which would impact the rheological tests.

(32) TABLE-US-00002 TABLE 1 Coal particles Wood particles Ash content (wt. %) 7.6 0.6 Moisture content (wt. %) 4.0 5.75 Volatile matter (wt. %) 36.2 72.8
B. Pretreatment of Wood Slurry

(33) In an actual working example, a portion of the prepared wood particles within the particle size of 150 μm-250 μm were pretreated using a proprietary method developed by our laboratory. The wood particles were mixed with water at solid weight percentages of 20 wt. %, 30 wt. %, and 40 wt. %. The mixtures were then heated at 230° C. at 100 psi of hydrogen for 30 min. The process was carried out in a sealed batch reactor; thus the difference in the solid content before and after the pretreatment was assumed to be negligible and was confirmed by thermal analysis of the biomass slurry after pretreatment. The 20 wt. % pretreated biomass slurry was then mixed with up to 35 wt. % of the 0-150 μm coal particles to form commingled biomass-coal-water slurries.

(34) Although 20 wt % pretreated biomass slurry was mixed with up to 35 wt % of the 0-150 um coal particles, it is also possible to use 30 wt % or 40 wt % wood particle preparations. Further mixtures can be heated at a range of between 180-300° C. at between 100-1000 psi of hydrogen for between 10-45 minutes. Also, although 35 w % of the 0-150 um coal particles were used, it is possible to use instead 150 μm-250 μm and 250 μm-500 μm size particles.

(35) C. Determination of the Slurry Rheological Properties

(36) Rheological properties of slurries were determined by using an Anton Paar Reolab QC rotational rheometer with temperature control. The rotational rheometer is a coaxial-cylinder rheometer with the center rotor rotating at a defined speed or torque. A six-blade vane spinner with 1 inch outside diameter was utilized as the rotor. The reason for employing a vane spinner as the rotor is that the vane-cup system causes much less error when testing large particles and has less impact on the slurry structure [9].

(37) Pump selection for handling slurries for industry applications is based on rheological data that are obtained from slurry rheology tests. The crucial parameters for pump selection are shear stress at certain shear rates, viscosity of the slurry, yield point, and settlement rate of the slurry. Other physical properties such as attrition and the friction of particles inside the slurry may also need to be considered for pump selection. The shear rate and shear stress curve of coal-water and wood-water slurry coordinates can be characterized by the Generalized Bingham Plastic model [10] as shown in Eq. 1. where τ is shear stress applied to the system when the shear rate of γ is maintained. τy is the yield stress of the starting slurry. K and n are empirical parameters determined by fitting the equation with experimental data. The correlation between shear rate and shear stress corresponds to a power law with constant coefficient of K. Thus, the viscosity of the slurry is defined as the slope of change in shear rate with a change in shear stress as given by Eq. 2. A change in viscosity can be obtained by either shear thinning or shear thickening. In shear thinning flow the viscosity decreases with increasing shear rate, while in shear thickening flow, viscosity increases with increasing shear rate.

(38) $\begin{array}{cc}\tau ={\tau }_y+K{\gamma }^n& \left(\mathrm{Eq}.1\right)\\ \mu =\frac{\Delta \tau }{\Delta \gamma }& \left(\mathrm{Eq}.2\right)\end{array}$

(39) Results and Discussion of Experiment 5

(40) A. Effect of Shear Rate on Viscosity

(41) The effect of an increase in shear rate on slurry viscosity was evaluated for different particle sizes and solid loading for both coal-water and wood-water slurries. The relationship between shear rate and viscosity was obtained for different particle sizes for coal-water and wood-water slurries. The results are shown in FIG. 3 and FIG. 4, respectively. The solid loading in the coal-water and wood slurries was fixed at 60 wt. % and 10 wt. %, respectively.

(42) Non-Newtonian shear thinning was observed for both coal-water and wood-water slurries. The viscosity of the coal-water slurries, shown in FIG. 3, decreased rapidly with increased shear rate up to 200 s.sup.−1 but then reduced at a slower rate beyond 200 s.sup.−1. Also, larger particle sizes had lower slurry viscosity. A similar trend was observed in wood-water slurries tests as seen in FIG. 4. The viscosity of wood-water slurries decreased rapidly with increased shear rates of up to 100 s.sup.−1 but decreased at a slower rate beyond 100 s.sup.−1. Similar to the coal-water slurries, the viscosity decreased with increasing particle size. A comparison of these two figures show that much higher shear thinning properties was observed for wood-water slurries. A possible reason may be that water is highly hydrogen bonded with wood particles. Therefore, higher shear stress was needed for wood-water slurries to maintain a same shear rate compared to coal-water slurries.

(43) B. Effect of Solid Content

(44) The maximum solid loading in coal-water and wood-water slurries varied for different particle size. When the maximum solid loading was exceeded, the mixture was not uniform as slurry and particles bound together to form larger particles. Table 2 shows the maximum solid loading for coal-water and wood-water slurries.

(45) TABLE-US-00003 TABLE 2 Maximum solid loading in wood-water and coal-water slurries Maximum wood loading Maximum coal loading in slurry (wt. %) in slurry (wt. %) 0-150 μm 13% 65% 150 μm-250 μm 13.5%   66.5%   250 μm-500 μm 15% 68%

(46) Experimental results for different solid loading on coal-water and wood water slurries are shown in FIG. 5 and FIG. 6, respectively.

(47) It can be seen from FIG. 5 that the coal-water slurries changed from a shear thinning property to a shear thickening property as the coal-loading decreased from 50 wt. % to 45 wt %. The shear thickening property of coal-water slurry was rarely observed by other studies. S. K. Majumder reported [11] that the reason for the thickening was due to the emulsion-solids exhibiting dilatants flow behavior with low solid loading range. It is also seen that the viscosity of coal-water slurries increased with increasing solid loading. There was not much difference between slurries with solid loading of less than 55 wt. % for shear rates over 150 s.sup.−1. Similar to the coal-water slurries, the viscosity of wood-water slurries also increased with increasing solid loading. However, at a shear rate over 100 s.sup.−1, Newtonian fluid properties were observed at solid loading less than 7.5 wt. % and the viscosity increased slightly with increasing shear rate, as shown in FIG. 6.

(48) C. Properties of Pretreated Wood-Water and Commingled Wood-Coal-Water Slurries

(49) The effect of shear rate on viscosity in pretreated wood-water slurry was also evaluated. FIG. 7 shows the rheological properties of pretreated biomass slurries with weight percentages of 20%, 30% and 40%. Unlike the wood-water slurry before pretreatment, the viscosity profile of pretreated wood-water slurry dropped rapidly as shear rate increased from 10 s.sup.−1 to 200 s.sup.−1, then decreased slightly beyond 200 s.sup.−1. The viscosity increased with increasing solid loading which is consistent with wood-water slurry before pretreatment. The important result is that with pretreatment there is an increase in the solid loading of wood-water slurry to 40% as compared to 12.5% before pretreatment. It is believed that presence of hydrogen under up to 230° C. and 100 Psi help break down the cellulose and semi-cellulose structure of wood which resulted in breaking the hydrogen bond between the wood and water. However, no analytical experiments were performed to confirm this.

(50) FIG. 8 shows the comparison of the viscosity of slurries with increasing solid loading. It is clear that the pretreatment process greatly helped increase the solid content in wood-water slurry at a similar viscosity. At the same viscosity, the coal-water slurry had the highest solid content. The commingled coal in pretreated wood-water slurry had a solid content up to 55 wt. %.

(51) D. Solid Loading of Pumpable Slurries

(52) We have found that a viscosity of less than 0.7 Pas is preferred for easy pumping of slurries to our reactor. We successfully increased the solid loading in the wood-water slurry by using our pretreatment method while maintaining the viscosity. The solid loading of pretreated wood-water slurry under 0.7 Pas was less than 35%. We commingled the pretreated wood-water slurry with coal to increase its solid loading and carbon content. The results of viscosity with increased solid loading of coal-water, wood-water, pretreated wood-water and commingled coal-wood water slurries are shown in FIG. 8. It is shown that at 0.7 Pas viscosity, coal-water slurry had the highest solid loading of up to 65%, and wood-water slurry before pretreatment had the lowest solid loading of less than 12.5%. After pretreatment, the solid loading in wood-water slurry of 0.7 Pas increased to nearly 35% and when commingled with coal, the solid loading increased to nearly 45%. Closer investigation of the water to carbon ratio of these slurries further suggested that the commingled coal-wood water slurry provided a water to carbon ratio of 2:1. With our gasification process the optimized water to carbon ratio is 3:1. Thus, with pretreatment, the rheological properties of the commingled coal-wood water slurry are improved for use as a feedstock for gasification. Such commingled coal-wood water slurries can be adjusted with water to obtain the desired water:carbon ratio of 3:1.

(53) Table 3 shows the results of mass based water to carbon ratio of different slurries at a viscosity of 0.7 Pas.

(54) TABLE-US-00004 TABLE 3 Mass based water to carbon ratio of slurries (0.7 Pas viscosity) wood- pretreated coal-water water wood-water commingled biomass- slurry slurry slurry coal-water slurry Ratio 0.78 13.82 3.67 2.01

(55) The viscosity plot of different water carbon ratio in commingled coal-wood water slurry is shown in FIG. 9. Under optimized water to carbon ratio of 3:1 for application as feedstock in gasification process, slurry viscosity is less than 0.45 Pas and provides good pumpability.

(56) In conclusion, our results show non-Newtonian properties of slurries and shear thinning behavior for most cases except the coal-water slurries with a solid content below 45%. Comparison of the viscosity of slurries under shear rate of 100 s.sup.−1 shows that thermal pretreatment increased the solid loading of wood-water and commingled coal-biomass-water slurries for the same viscosity values. Pretreatment of the commingled coal-wood slurries provided a pumpable slurry with a solid carbon content for optimum feed to the steam hydrogasification reactor.

(57) Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process and apparatus described in the specification. As one of ordinary skill in the art will readily, appreciate from the disclosure of the present invention, processes and apparatuses, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized according to the present invention. Accordingly, the appended claims are intended to include such processes and use of such apparatuses within their scope.

REFERENCES ALL OF WHICH ARE INCLUDED BY REFERENCE IN THEIR ENTIRETY

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