EP2925424A1

EP2925424A1 - Process for drying wet gas with desiccants and for regenerating the desiccants with syngas for implementing water gas shift

Info

Publication number: EP2925424A1
Application number: EP13820954.9A
Authority: EP
Inventors: Geert Haarlemmer
Original assignee: Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Current assignee: Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Priority date: 2012-11-29
Filing date: 2013-11-27
Publication date: 2015-10-07
Also published as: WO2014083517A1; FR2998483A1

Abstract

The invention relates to a process and equipment for drying wet gas by means of desiccants and for regenerating the desiccants, the process comprising the following steps: • a) adsorption of the water contained in a wet gas by circulating said gas on at least one bed of desiccants, • b) regeneration of the desiccants by circulating a syngas on the at least partially saturated desiccants so as to implement the reaction known as water gas shift.

Description

METHOD FOR DRYING HUMID GAS WITH DESSICANTS AND REGENERATING DESSICANTS WITH SYNTHESIS GAS FOR IMPLEMENTING WATER GAS REACTION

Technical area

The present invention relates to a method of drying wet gas by means of desiccants and desiccant regeneration according to which adsorption of water contained in a wet gas is carried out by circulating it on at least one bed of desiccants.

A preferred application aimed at is the drying of biomass and, more generally of carbonaceous material feedstock, in a thermochemical conversion process with a view to producing a fuel or a fuel, in particular a liquid fuel, or another product of synthesis by gasification in a gasification reactor.

Another preferred application is the forced drying of organic waste to form compost.

The invention makes it possible to increase the energy efficiency of the wet gas drying process in itself and more particularly to increase the energy efficiency of a global process incorporating the drying process, such as a thermochemical conversion process of biomass by gasification.

Although described below with reference to a gasification production of a charge of carbonaceous material, the synthesis gas (mixture of carbon monoxide and hydrogen) used in the process according to the invention can also be produced by methane reforming or by partial oxidation of methane.

Likewise, although described with reference to humid ambient air, the drying method according to the invention can equally well be implemented for a natural gas.

It is specified here and in the context of the invention that "ambient air" means the usual meaning of the expression, namely air directly from the external environment.

State of the art

In many industrial sites, it is necessary to dry a wet gas, including ambient air. Notable industrial sites include thermochemical biofuel (BtL) plants, composting sites, as well as drying facilities for wood or other products.

Composting of biomass is a slow degradation by aerobic microorganisms. This process can be done either in a building for industrial composting, under relatively controlled conditions, or in a typical pile in a garden, under less well-controlled conditions. In the case of composting in a building, outdoor air more or less cold and wet depending on the season and the hours of the day is allowed in the building and is extracted permanently to be rejected after cleaning. The compost is sifted then sold. Sieving rejects are landfilled or burned in an incinerator. When air reaching and present in the building is cold and very humid, the air can not absorb the water released by the compost. Also, it is difficult to dry the mixture, and in fact the compost remains wet and sieving is more difficult to achieve. Sometimes a thick fog may be formed causing more than delicate working conditions.

The so-called "Biomass to Liquid" factories, designated by the acronym BtL, are factories intended to implement a process for the thermochemical conversion of biomass by gasification in order to produce a liquid fuel. These BtL plants have already been widely described with a large number of economic data both in investment and production cost: [1], [2]. The BtL plants that are currently being designed are demonstration projects that aim to test and validate the entire technological chain of the thermochemical conversion process. The first stage of implementation or process in its own right consists of drying the wet biomass. In fact, the moisture of freshly collected biomass is typically between 30 and 50%, this initial rate of humidity varying according to the type of biomass, the collection period and the location where the biomass is stored.

It has already been proved that the water contained in the biomass greatly reduces the gasification yield because it involves the generation of unnecessary water vapor and evaporation of the water required in the gasification reactor. In addition, it is already recognized that the natural drying of biomass can not really be considered in an industrial application given the time required: [3], [4], [5]. In other words, on an industrial scale only forced drying of biomass can be considered. It also seems to be accepted that the drying of lignocellulosic biomass below a moisture content of about 15% proves useless because below this value the wood proves to be very hygroscopic and re-adsorbs the water when exposed to air during its transfer to the gasification reactor and its intermediate storage. In addition, the extraction of the last percent moisture significantly increases energy consumption. Thus, it seems accepted that a drying of the biomass at around 15% moisture content prior to its gasification is a good compromise in terms of efficiency of conversion efficiency and energy consumption required.

For the actual biomass drying operation, many technologies have already been tested: [6]. These technologies can be broadly classified into two categories depending on the nature of the heat source used in the driers: air or hot smoke or water vapor. The technology used depends largely on the heat source available. One type of dryer widely considered for drying wood for gasification is a conveyor belt dryer. The wood, typically in the form of chips or chips of unit dimensions of the order of 1 to 5 cm is conveyed on conveyor belts. Hot air is brought into contact in the thickness of the wood conveyed in general by blowing against the current but also by current through the thickness of the wood layer conveyed through the conveyor belts. As currently envisaged, the air is the ambient air taken from the outside environment and is heated to about 130 ° C, often by water vapor. This method of drying wood is long and consuming a lot of energy because of the very large amount of hot air required. Thus, the wood drying process currently envisaged is expensive, more particularly in energy. After the gasification, the synthesis gas (containing carbon monoxide, hydrogen, among others) is mixed with water vapor and passed over a gas reactor to the water to increase the hydrogen content (CO + H2O -> CO2 + H2). This exothermic reaction consumes a lot of water vapor which represents a considerable cost of production in a plant.

More generally, there are many technologies for drying air or other gases. On the industrial scale, several solutions exist that can be detailed as follows. Air dryers, known as refrigerators, work by compressing the air and then cooling the compressed air to a temperature below its dew point. For relatively small capacities, cooling is provided by Peltier machines. For larger capacities, cooling is done by integrating a heat pump [7]. With such driers, the dew point temperature is generally 2 ° C or 10 ° C. The inventor considers that to be really advantageous, such driers must have a dew point of the air dried at a temperature of the order of -20 ° C. This implies a significant energy cost.

The drying of the air by means of absorption machines, in particular those coupled to a solar collector, has already been envisaged. To date, it has been found that cooling of the air by 30 ° C to 20 ° C is possible, but being able to go down to a temperature of -20 ° C is not certain. It is therefore difficult to evaluate the real energy cost [8].

It is also known to dry natural gas by absorption in a glycol column, generally used under pressure. A glycol (triethylene glycol, TEG) wash is effective for a gas under pressure to obtain a very dry gas. This solution is the reference as a high pressure natural gas dryer with very low dew points around -20 ° C. Its use at low pressure remains to be demonstrated, and the electrical power required for regeneration has not been evaluated.

Finally, it is known to dry the air by adsorption by circulating a flow of air to be dried on desiccants, such as so-called activated alumina, zeolites or a silica gel known as silica-gel.

The so-called activated alumina is produced by de-hydroxylation and in particular has the characteristic of being porous or even very porous, typically with a specific surface area of between 50 and 400 m ² / g, which gives it a high adsorption capacity. The air drying with activated alumina is for example described in patent applications EP0039504 and EP0922482 and in publications [9], [10]. Activated alumina is in the form of beads. Two activated alumina beds are generally used for air drying, one for moisture absorption and the other for regeneration. The regeneration can be done either by depressurization (PSA) or by temperature variation (TSA, acronym for "temperature swing adsorption"). As indicated in the publication [9], regeneration Thermal, usually made with a source of hot air, is made at 160 ° C dry gas, or 220 ° C wet gas. The major advantages of activated alumina air drying are its reliability and efficiency in drying air to dew points at very low temperatures. On the other hand, the regeneration of activated alumina requires a lot of energy: [11].

Thus, it appears that in all existing air drying technologies, the energy cost is important either in direct electrical energy or in thermal energy for the regeneration of the sorbent (adsorbent or absorbent).

Furthermore, it is known from the patent application WO 2010/059055 that alkaline doped alumina can adsorb acid gases such as H 2 S and / or catalyze the so-called water gas reaction (WGS). water gas shift ") at a temperature around 400 ° C. In this patent application, it is stated that the water required to implement the WGS reaction is either provided by steam or already contained in the gas.

The general object of the invention is to overcome at least some of the disadvantages of the state of the art of drying a wet gas, more generally humid ambient air, in particular by reducing the energy cost required.

A particular aim is to propose a method for drying wet gas which makes it possible to increase the energy efficiency of a global process incorporating said drying process, such as a method of thermochemical conversion of the biomass by gasification.

Presentation of the invention

To do this, the subject of the invention is a method for drying wet gas by means of desiccants and regeneration of desiccants, comprising the following steps:

a / adsorption of the water contained in a wet gas by circulating it on at least one bed of desiccants,

b / regeneration of desiccants by circulating a synthesis gas on desiccants saturated at least partially so as to implement the so-called reaction reaction of water gas (WGS acronym for "Water Shift Gas") between the water from saturated desiccants and carbon monoxide CO present in the synthesis gas. It is specified that in the context of the invention the flow of synthesis gas on saturated desiccants can be done with both desiccants fixed bed or themselves circulating bed. In this latter variant, the desiccants can thus circulate in co-current with the synthesis gas or against the current of the latter in a reactor.

In other words, according to the invention, the WGS reaction is carried out on desiccants already loaded with water, instead of implementing the WGS reaction by introducing into a dedicated reactor, a mixture of water vapor and carbon dioxide gas. synthesis (syngas).

Thanks to the invention, it reduces the energy cost of air drying compared to state of the art techniques because it is not necessary to produce as much water vapor and reduces the amount of air required in the biomass dryer.

The process is particularly advantageous in a general gasification thermochemical conversion process in which it is necessary both to dry air to dry the input bio mass and to carry out the WGS reaction downstream of the gasification reactor. The synthesis gas from the gasification can be cooled to the appropriate temperature, preferably around 200 to 250 ° C, to regenerate the desiccants. The carbon monoxide then reacts with the water present in the desiccants to form CO2 carbon dioxide, H2 hydrogen and heat. The heat is consumed to release the adsorbed water in desiccants. No other source of heat is needed for regeneration.

It may, however, be necessary to add an additional unit to implement an additional WGS reaction to that just described for the regeneration of desiccants, in order to obtain a precise ratio [H2] / [CO]. Indeed, on the one hand the ratio [H2] / [CO] obtained at the outlet of a gasification reactor is variable according to the type of reactor: with water vapor as a gasifying agent, it is thus generally between 1: 0.7 and 1: 1 at the outlet of a driven flow reactor and greater than 1: 1.5 in a fluidized bed reactor. On the other hand, the ratio [H2] / [CO] necessary for the implementation of the synthesis of a fuel or other synthesis product must be precise and it varies according to the type of synthesis reaction. Typically, for a Fischer-Tropsch synthesis, the input ratio [H2] / [CO] must be equal to 2.1: 1. Thus, a further WGS reaction to that causing the regeneration of the desiccants can be advantageously provided to obtain an exact ratio [H2] / [CO] necessary for the synthesis of a liquid fuel or synthetic product. The desiccants according to the invention are preferably chosen from an activated alumina, a zeolite, a silica gel or an activated carbon.

Of these, activated alumina is still preferred. Indeed, activated alumina inherently has a considerable adsorption capacity, without the regeneration according to step b / is complicated. Another advantage of using alumina is the ease with which it is doped or loaded with a catalyst that facilitates the reaction of gas with water. Thus, for example, for a flow rate of 200 kNm ³ / h with a 100% humid air at 10 ° C, conditions frequently encountered in winter in France, it is necessary to capture a quantity of 1600 kg / h of water to descend to a dew point at -20 ° C, without the need to cool the air: the relative humidity of the air then drops to a value of the order of 10%. With a variation of the amount of water on activated alumina of between 10 and 30%, that is to say an amount of between 10 and 30 grams per 100 grams of alumina, it is necessary to have an amount of 8000 kg alumina per hour. In the publication [1 1] above, it is indicated an estimate of the adsorption energy of activated alumina at 3000 kJ / kg, or 130% of the latent heat. This implies having a quantity of energy of 1.3 MW to evaporate the water to which must be added the sensible heat necessary to heat the alumina (Cp = 1000 J / Kg / K). With the necessary amount of alumina indicated above, ie 8 tons of alumina per hour, the heat energy required to heat the alumina is about 380 kW at a heating temperature of the order of 200 ° C. commonly available at the outlet of the gasification reactor. The energy required for the regeneration of activated alumina can therefore be estimated at about 1.7 MW, a value that can be fully provided by the WGS reaction.

According to a preferred variant, step b / is carried out by activated alumina impregnated with a catalyst.

Preferably, the catalyst is based on molybdenum sulphide (MoS), cobalt and molybdenum sulphide (CoMoS) or iron oxide. These catalysts have the advantage of being oxidized at temperatures much higher than those at which the regeneration step b / is carried out. The catalyst can be advantageously chosen for its resistance to H ₂ S in the synthesis gas if it is present, thereby avoiding an expensive purification step. Cobalt and molybdenum sulphide (CoMoS) is particularly advantageous since it is resistant to PH ₂ S, active at temperatures around 200 ° C., and inexpensive. It is It is also possible to catalyze the WGS reaction according to step b / with alumina doped with alkaline salts at a temperature around 400 ° C.

The steps a / and b / of the process according to the invention can be carried out continuously or discontinuously.

Advantageously, continuously, the desiccants can circulate in the form of a fluidized bed, and advantageously still on a fixed bed of catalyst.

Desiccants, such as activated alumina, are preferably in the form of beads, which allows easier circulation.

Step b / is preferably carried out with a synthesis gas whose temperature is between 160 ° C. and 250 ° C., preferably at about 200 ° C., temperatures that can easily be reached by cooling at the outlet of the gasification reactor. .

According to an alternative embodiment, a cleaning step of the synthesis gas is carried out before or after step b /.

According to another variant embodiment, before step a / the desiccants are swept by circulating an inert gas, such as CO 2, nitrogen or another inert gas. Thus, the oxygen possibly present in the pores of desiccants / catalyst is removed avoiding any risk of explosion, by direct contact between the hydrogen contained in the synthesis gas and the oxygen of the air.

The synthesis gas of step b / according to the invention can be produced by reforming methane or by partial oxidation of methane or gasification of a carbonaceous material feedstock.

The wet gas that can be dried according to the invention can be either a natural gas or ambient air.

The synthesis gas from step b / can then after possible purification, be used for the production of hydrogen, in the synthesis of fuels (bio-fuels) or be used to make electricity in an engine or turbine gas.

The advantages of the air drying process just described are numerous and can be listed as follows:

- simplicity of drying the air,

simplification of the drying / regeneration of desiccants compared to the processes according to the state of the art, reduction of thermal losses compared to drying processes according to the state of the art because the heat released by the WGS reaction is brought directly to the core of the process,

reducing the consumption of water vapor for injection into a synthesis gas for implementing the WGS reaction,

possible reduction of the sizing of the biomass dryer, possible reduction of the drying air flow required for the drying of the biomass,

possible increase in hydrogen production, downstream of a gasification reactor,

possible increase in C0 ₂ production downstream of a gasification reactor, for sequestration or recovery purposes,

possible sequence of the WGS reaction according to step b / in a complete plant for the production of hydrogen, or for the production of liquid biofuels.

The invention also relates to a method of forced drying of organic waste intended to constitute compost, by means of the ambient air dried in accordance with step a / of the method which has just been described.

The invention also relates to a process for the thermochemical conversion of a feedstock of carbonaceous material into a synthesis gas for producing a fuel or a fuel, in particular a liquid fuel, or another synthetic product, comprising the following steps:

forced drying of a carbonaceous material charge by means of the ambient air dried in accordance with step a / of the drying process described above,

- gasification of the charge in a gasification reactor,

step b / of the drying process described above, with the synthesis gas produced upstream by the gasification in the reactor.

The charge of carbonaceous material is preferably lignocellulosic biomass.

The gasification reaction can be carried out at temperatures comprised

700 and 1600 ° C. According to an alternative embodiment, the gasification reactor is a fluidized bed type reactor, the gasification reaction being carried out at temperatures between 800 and 950 ° C.

According to an alternative variant, the gasification reactor is a flow-type reactor driven, the gasification reaction being carried out at temperatures between 1200 and 1600 ° C.

According to an advantageous embodiment, a synthesis according to the Fischer-Tropsch process followed by hydrocracking is carried out downstream of step b / to produce liquid fuel of the diesel or kerosene type.

The invention finally relates to an installation continuously implementing the method (s) described above, comprising:

a first reactor whose inlet is connected to a wet gas circuit

a second reactor, the inlet of which is connected to a synthesis gas circuit; circulating means for circulating the desiccants respectively inside the first reactor, from the first reactor to the second reactor and vice versa; versa, and inside the second reactor, so as to implement the adsorption of the water contained in the wet gas in the first reactor, the regeneration of desiccants by the synthesis gas on desiccants saturated at least partially and the so-called WGS reaction of gas-to-water reaction between the carbon monoxide present in the synthesis gas and the water present in the desiccants in the second reactor.

According to an advantageous embodiment:

desiccants are in the form of beads,

the first and second reactors are arranged vertically, the circulation means inside the first reactor comprise guides without a catalyst, fixed inside the first reactor, to allow gravity circulation of the balls from the upper part from the first reactor in which they are unsaturated to the lower part of the first reactor in which they are saturated,

the circulation means of the first reactor to the second reactor comprise a first fluidization device of the balls, connected on the one hand to the first reactor and on the other hand to the second reactor by a pneumatic transfer line, the circulation means inside the second reactor comprise guides containing catalysts, fixed inside the second reactor, to allow gravity circulation of the balls from the upper part of the second reactor in which they are saturated up to the lower part of the first reactor in which they are regenerated,

the circulation means of the second reactor to the first reactor comprise a second fluidization device for the balls, connected on the one hand to the second reactor and on the other hand to the first reactor by a pneumatic transfer line comprising at least one pressurized transfer chamber to store the regenerated balls under pressure.

detailed description

Other advantages and features of the invention will emerge more clearly from a reading of the detailed description of the invention, given by way of illustration and without limitation with reference to the following figures among which:

- Figure 1 is a schematic view of the principle of a part of a thermochemical conversion of carbonaceous material feed gasification continuously implementing a drying process according to the state of the art;

Figure 2 is a schematic view of the principle of a part of a thermochemical conversion of carbonaceous material feed gasification continuously implementing a drying process according to the invention;

FIG. 3 is a detailed view showing an advantageous embodiment of a continuous installation according to FIG. 2.

In the description which follows the terms "input", "output" "upstream", "downstream", are used by reference with the directions of transfer of biomass, circulation air and synthesis gas in the facilities of thermo chemical conversion by gasification. It is pointed out that the arrows shown in FIGS. 1 and 2 precisely indicate these directions of biomass transfer and circulation of gases.

For the sake of consistency, the same reference numerals designate the same elements of the installations according to the invention and according to the state of the art.

It is also specified that the term "reactor" used hereinafter may relate to several reactors operating in parallel. An example of a continuous installation employing a thermochemical conversion by gasification according to the state of the art, as a comparative example, and an example 1 according to the invention, is described below. It should be noted that only a part of the installations are represented and that they may include many other units, such as a roasting unit for dried biomass, a roasting unit for roasted biomass, cooling systems for heat exchangers. heat such as those at the outlet of the gasification reactor, cleaning devices and / or purification of the synthesis gas downstream of the gasification reactor.

The comparative example of the installation according to the state of the art is shown in FIG. 1, whereas example 1 relating to the installation according to the invention is represented in FIG.

Firstly, the elements common to the two installations 1, respectively according to the state of the art (FIG. 1) and according to the invention (FIG. 2) are described.

The continuous installations 1 represented each implement a method of a gasification of biomass for the synthesis of a synthetic fuel. Thus, lignocellulosic biomass originating from a suitable storage tank (not shown) continuously feeds a biomass dryer 2 of the conveyor belt type.

Then, the dried mass biomass feeds continuously a gasification reactor 3, type circulating fluidized bed (FICFB, acronym for "Fast Internai Circulating Fluidized Bed").

Moreover, the fluidized bed reactor 3 can preferably operate between 800 and 950 ° C. and at pressures approximately of the order of atmospheric pressure. The reactor 3 can also be a driven flow type reactor (RFE), preferably operating at temperatures typically between 1400-1600 ° C and at high pressures, typically between 5 and 80 bars.

At the outlet of the gasification reactor 3, a raw mixture of synthesis gas comprising, for the majority species of CO, C0 ₂ , H ₂ 0 and H _2, is emitted. Thus, in general, a bio mass gasification in a driven flux reactor 3 without addition of steam produces a synthesis gas containing about 50-70 mol% CO, 3-15 mol% H 2, 1-8 mol% CO 2 and the like. -35 mol% H 2 O. The synthesis gas is cooled after the reactor in the heat recuperator to be usable downstream. It is specified that the exchanger adapted to cool the gas is integrated in the gasifier and is not shown as such in the figures.

Downstream of the gasification reactor 3, there is arranged a reactor 4 adapted to perform the gas-to-water reaction (WGS). Thus, at the outlet of the reactor 4, a synthesis gas is emitted with a ratio [H2] / [CO] necessary for the synthesis of a liquid fuel or synthesis product, in particular for a liquid fuel obtained by Fischer Tropsch synthesis.

In the bio mass dryer 2, it is dried by drying air. In order to obtain the drying air, the ambient air is sent to a heater 5 and is heated by low pressure steam. Thus, the air leaving the heater 5 has a relative humidity decreased compared to the ambient air entering the heater 5. A low pressure condensate also exits the heater 5.

The installation 1 according to the invention (FIG. 2) differs from the installation according to the state of the art (FIG. 1) in that it furthermore comprises:

a reactor 6 whose inlet is connected to the ambient air and the outlet is connected to the heater 2,

a reactor 7 whose inlet is connected to the outlet of the gasification reactor 3 and the outlet is connected to the reactor 4 for implementing the WGS reaction.

The reactor 6 is filled with a bed of activated alumina beads, comprising a catalyst or not, to carry out a step a / adsorption of the water contained in the ambient air. Thus, compared to the example according to the state of the art, the ambient air is dehydrated before being heated by the low pressure steam. Thus, according to the invention, because of drier air entering the dryer 2, the drying kinetics of the biomass are faster at the beginning and identical at the end (identical humidity level). Drier air input has greater drying capacity in the dryer.

The reactor 7 is regularly filled with a bed of activated alumina beads saturated beforehand in the reactor 6 to perform a step b / of regeneration of the balls, provided with a catalyst or not, by circulating the synthesis gas from the gasification reactor 3 on said saturated beads so as to also implement the so-called reaction reaction of water gas (WGS acronym for "Water Shift Gas"). The two saturated and regenerated activated alumina beds are exchanged at regular time intervals. The synthesis gas from the gasification reactor 3 and which enters the regeneration reactor 7 of activated alumina beads has a temperature around 220 ° C.

A simulation of the thermodynamic operating conditions of the two installations 1 that have just been described was carried out using ProSim Plus ® industrial process simulation software: [12].

In both installations, the entry conditions from actual conditions are as follows:

ambient air at 10 ° C. with a relative humidity of the order of 70%, desired dried biomass flow rate at the exit of the dryer 2: 100 t / h (representing 500 MW thermal),

temperature of the air heated by the low-pressure steam (at the heater outlet 2): 123 ° C,

alumina slightly adsorbed at a ratio of 10 to 30%> of its mass in water. For the calculation, here we assume a variation of 20% between the regenerated state and the saturated state. The density is typically 800 kg / m ³ .

The simulation results are given in Table 1 below:

TABLE 1

Example Example 1 according to the state of the art according to the invention

(Figure 1) (Figure 2)

Humidity in ambient air in 0.0053 kg water / kg air 0.0053 kg water / kg dry air dry inlet

Humidity in the inlet air of 0.0053 kg water / kg air 0.0015 kg water / kg air dryer 2 sec dry

Quantity of water to be removed from the air 5.5 m ³ / h

Amount of alumina required 27 t / h (34 m ³ / h)

Required air flow input 1607 kNm ³ / hr 1131 kNm ³ / hr

Low pressure steam flow 105.2 t / h 73.5 t / h needed

Required heating capacity 66.5 MW 46.4 MW

Concentration rate of water in 2.75%> mass 2.75%> mass air output of dryer 2

Air temperature at the outlet of 50 ° C 50 ° C dryer 2

Ratio H ₂ : CO at the reactor inlet 4 1: 0.76 1: 1.31 It can be seen from Table 1 that the invention has the major advantage of reducing the air flow required at the dryer inlet 2, which has a reduction in the consumption of the low-pressure water vapor to be used for drying. The low pressure water vapor economy, as simulated, is equal to about 31 t / h, which represents about 20 MW of heat consumption. Relative to the total power required for the comparative example according to the state of the art, ie 500 MW, the economy of low-pressure water vapor consumption represents 4%. Considering an average yield equal to 25% for a steam turbine, the gain in water vapor can bring about a gain in electricity of about 5 MW.

On the other hand, even if it is not indicated in Table 1 above, step a / adsorption of water by activated alumina releases substantially heat. This released heat can be reasonably estimated at about 3.5 MW.

Finally, the heat of the same order of magnitude is 3.5MW required to perform the step b / regeneration can be fully provided by the WGS reaction.

The results and advantages of an installation according to the invention are of course dependent on the ambient temperature and humidity conditions. Also, these conditions were varied to quantify the energy gain in different configurations. Table 2 below shows the results obtained for ambient air with relative humidity levels respectively of 50%, 70%>, and 90%> and temperatures respectively of 0 ° C, 10 ° C and 20 ° C .

TABLE 2

Example Example 1 Difference according to the state of the art according to the invention of

(figure 1) (figure 2) required power

Conditions Flow Power Ratio Flow Power Ratio Gain

H2 / CO e e H2 / CO ambient air e obtained

Temperature (kNm ³ / h) heats up in (kNm ³ / h) heats up according to

(° C) required input required input the invention

- (MW) of (MW) of (MW)

Reactor reactor rate

of humidity 4 4

relative (%>)

0 ° C-50% 1384 62.1 0.76 1412 49.1 1.12 13

0 ° C-90% 1481 66.5 0.76 1438 49.9 1.2 16.6 10 ° C-50% 1500 61.9 0.76 1441 46 1.22 15.9

10 ° C-70% 1607 66.5 0.76 1459 46.4 1.31 20.1

10 ° C-90% 1723 71.3 0.76 1473 46.8 1.4 24.5

20 ° C-50% 1765 66.6 0.76 1478 42.8 1.45 23.8

20 ° C-70% 2056 77.8 0.76 1499 43.3 1.7 34.5

20 ° C-90% 2475 93.9 0.76 1515 43.6 1.99 50.3

It can be seen from Table 2 that the required power gain obtained thanks to the invention is proportional to the relative humidity level and the ambient air temperature. The energy gain is mainly due to the lower airflow required because the air has a high adsorption capacity of water.

It can also be seen that the temperature has less impact than the relative humidity level.

It can be concluded that an installation according to the invention (FIG. 2) requires less heat for the production of liquid fuel than a plant according to the state of the art (FIG. 1) and that the energy gain obtained depends on the temperature and pressure conditions of ambient air, which is the input gas for biomass drying.

In view of the simulations carried out, it is possible, thanks to the invention, to save on the order of 10 to 50 MW of thermal power for a plant producing liquid fuel from biomass currently dimensioned with a total thermal power of 500 MW. With a steam turbine efficiency of about 25%, these thermal energy gains can lead to the production of an electrical power of the order of 2 to 12MW, which can reduce operating costs. of such a factory.

Example 2

The following example 2 is carried out as for the installation of FIG. 2 but with data from real conditions as they exist to date for a liquid fuel production plant from lignocellulosic biomass initiated. by the plaintiff with industrial partners. This example 2 also makes it possible to give an indication of the quantities required for the activated alumina balls as desiccants and for the synthesis gas necessary for their regeneration.

A gasification of a flow rate of 2 tonnes of dry mass per hour produces a synthesis gas of composition 63 mol% CO, 13 mol% H2, 2 mol% CO2 and 23 mol% H2O and of sufficient quantity to consume 1600 kg / h of water from

200 kM ³ / h ambient air saturated at 10 ° C.

Currently, the input flow is equal to 15.5 t / h of lignocellulosic biomass, in the form of forest chips, having a relative humidity of 40%. This biomass is dried until it reaches a relative humidity of 15%, ie a flow rate of 10.8 t / h. The air required for drying is ambient air taken outside at 10 ° C and a relative humidity of 70%. The drying air is heated to

130 ° C and is contacted with the lignocellulosic biomass at a rate of 200 t / h.

The exit air of the biomass dryer thus exits at a temperature of 42 ° C. with a relative humidity level equal to 50%, ie 2.75% mass of water. Under these conditions, the drying of the biomass and thus the heating of the drying air requires a power of 6.4 MW of the low pressure water vapor.

With the installation according to the invention according to FIG. 2, the drying of the ambient air by adsorption of the water by the alumina balls can make it possible to go from a relative humidity of 70% to 20%. %, ie a condensation of a flow rate of 800 kg / h of water.

This condensation produces 0.5 MW of heat that can be returned to the air.

With a drying of the ambient air with an initial moisture content of 70% to 20%, 20g of water can be stored in 100g of alumina. Thus, it is possible to estimate the flow rate of alumina balls required at 4 tons per hour.

The activated alumina balls have a specific heat capacity Cp of the order of 1000 J / kg / ° C. Thus, with a synthesis gas from the gasification reactor 3 at a temperature of 200 ° C., the alumina balls in the reactor 7 have a temperature close to the inlet air temperature of 20 ° C. The heat stored in the alumina is about 0.15 MW and transferred to the air.

Thus, in the end, the drying of the ambient air generates 0.65 MW of heat produced during the regeneration of the alumina balls.

Moreover, at the outlet of the gasification reactor 3, a flow rate of synthesis gas of the order of 18,000 kg / h is available. However, the regeneration of saturated alumina balls with a flow rate of synthesis gas is of the order of 3000 kg / h, ie a proportion of 16% with respect to the available flow rate. In other words, it is necessary to have the reactor 4 downstream to perform the WGS reaction with all the flow of synthesis gas from the gasification reactor. The drying air flow rate in the biomass dryer 2 can be reduced by 15%, the drier air obtained according to the invention involving a smaller amount to dry more biomass.

The saving achieved by the invention on the air flow is 15% on a power requirement initially equal to 6.4MW, or about 1MW. This saving represents more than 2% of the total energy load of the plant which is 45MW.

An advantageous embodiment of circulation circulating bed of activated alumina beads is shown in FIG.

According to this embodiment, the respective reactors 6 for water adsorption and 7 for regeneration of the alumina balls are arranged vertically and are interconnected by circulation means described in detail below. Thus, the alumina balls circulate continuously by gravity in each of the reactors 6 and 7 and from one to the other passing from their saturated state to their regenerated state.

Guides 60 in the form of hollow parts, devoid of catalyst, are fixed inside the adsorption reactor 6.

A first device 8 for fluidization of the balls is connected on the one hand to the lower part of the reactor 6 and on the other hand to the upper part of the reactor 7 via a pneumatic transfer line 9.

Guides 70 containing catalysts are fixed inside the regeneration reactor 7. Preferably, the catalysts consist of cobalt and molybdenum sulphide (CoMoS) active at temperatures around 200 ° C, or substantially the temperature at which the synthesis gas from the gasification reactor 3 enters the reactor 7 .

A second device 10 for fluidizing the balls is connected on the one hand to the lower part of the regeneration reactor 7 and on the other hand to the upper part of the adsorption reactor 6 via a pneumatic transfer line 11.

On this pneumatic transfer line 11 is provided a pressurized transfer chamber 12 for storing the regenerated balls under pressure.

A valve 13 may be provided between the transfer chamber 12 and the inlet of the adsorption reactor 6 to regulate the flow of the balls entering the latter.

The operation of the continuous flow system of the alumina beads is as follows. The alumina balls circulate by gravity from the top to the bottom of the adsorption reactor 6 against the current of the humid ambient air to be dried. During their circulation in this reactor 6, the alumina balls adsorb the water contained in the ambient air, which dries it.

The saturated alumina balls are fluidized by the device 8 and sent to the upper part of the regeneration reactor 7. They circulate by gravity inside this reactor 7, while being regenerated by the synthesis gas from the reactor of gasification 3. The catalysts accelerate the regeneration so that in the lower part of the regeneration reactor 7 the balls are completely regenerated.

They are then fluidized by the device 10 and then sent into the transfer or storage chamber 12 by the pneumatic transfer line 11.

This results in a circulation operation of the alumina balls with a single circulating bed for a significant amount of saturation / regeneration cycles.

Example 3

The following example 3 is described in connection with an air drying installation before admission to a composting building. A major problem in composting buildings is the humidity of the air. The air drying according to the invention makes it possible here to facilitate the composting process. In other words, according to the invention, a forced drying of organic waste intended to constitute compost is carried out by means of ambient air dried by adsorption on a bed of alumina beads. The data given below are in part those of an existing composting facility.

Here, drying of the ambient air is carried out to obtain air at 30 ° C., saturated at 100% (0.027 kg H ₂ 0 / kg dry air) with a flow rate of 200 kNm ³ / h.

Screening rejects, ie quantities of organic waste that can not be used as compost after the sieving operation, can provide a thermal power of about 1.7 MW to burn them in a wet state , or 2.5MW after drying.

A quantity of approximately 1600 kg H ₂ 0 / h is required to remove air in order to have a dew point at a temperature of -20 ° C., which corresponds to an ambient air with 0.01 kgH 2 O / kg. dry air, ie a relative humidity of less than 10% at 10 ° C.

When step b / of regeneration is carried out with a synthesis gas resulting from the gasification of the sieving refusals, the water present in the saturated alumina balls reacts. with CO in the WGS reaction. This WGS reaction then releases a thermal power of about 1.3 MW.

This value corresponds to the heat necessary to evaporate the flow rate 1600 kg / h H ₂ 0 free. Also, the additional heat required is limited to the heating of the alumina and the difference between the heat necessary for the evaporation of the water and the drying of the alumina, that is to say 0, 4 MW. Thus, more than 90% water in the alumina is converted to hydrogen H2.

The regenerated hot alumina is cooled with ambient air during drying. A thermal power of 0.4 MW is used to heat the air. If this heat is dissipated in the air, with a flow rate of 200 kNm ³ / h and taking into account the specific heat capacity Cp of the alumina of the order of 1000 J / kg / ° C, the temperature of the air increases by 6 ° C.

This temperature increase of 6 ° C. is advantageous for the composting process.

Although described with reference exclusively to biomass the air drying system according to the invention and conversion into a fuel or a fuel, in particular a liquid fuel, or another synthetic product, the invention can be used to the conversion of other charges of carbonaceous material (coal, pet coke, organic waste ...).

References cited

[I]: Tijmensen MJA, Faaij APC, Hamelinck CN, Hardeveld MRM. "Exploration of the possibilities of Fischer Tropsch liquids and power via biomass gasification" Biomass & Bioenergy 2002; 23: 129-52.

[2]: Haarlemmer G, Boissonnet G, Imbach J, P-A Setier, Peduzzi E. "Second generation BtL type biofuels - a production cost analysis" Energy & Environmental Science 2012; 7.

[3]: Simpson WT. "Equilibrium Moisture Content of Wood in Outdoor Rentals in the United States and Worldwide". FPL-RN-0268. Forest Products Laboratory: Madison, Wisconsin, 1998.

[4]: Höldrich A, Hartmann H. "In Storage of wood logs -" Drying speed and dry matter losses ", 14th European Biomass Conference, Paris, France, 2005.

[5]: Scholz V, Idler C, Daries W "In Energy Loss and Mold Development During Storage of Wood Chips in Unventilated Piles", 14th European Biomass Conference, Paris, France, 2005.

[6]: Fagernas L, Brammer J, Wilen C, Lauer M, Verhoeff F. "Drying of biomass for second generation synfuel production", Biomass and Bioenergy 2010; 34: 1267-77.

[7]: Parker Hannifin Corporation's .pdf commercial brochure "Smart Cycle Plus (SCP) and Magnum Cycling Refrigerated Air Dry ers".

[8]: K. Sumathy, K.H. Yeung, Li Yong's "Technology Development in Solar Adsorption Refrigeration Systems," Progress in Energy and Combustion Science 29 (2003) 301-327.

[9]: Axens. "Air and Gas Drying with Activated Alumina".

[10]: Getty RJ, Armstrong WP. «Drying Air with Activated Alumina

Adiabatic Conditions ". Industrial & Engineering Chemistry Process Design and Development 1964; 3: 60-5.

[I I]: Srivastava NC, Eames IW. "A review of adsorbents and adsorbates in solid-vapor adsorption heat pumps systems". Applied Thermal Engineering 1998; 18: 707-14.

[12]: ProSimPlus, Version 3; ProSim company: Toulouse, France, 2011. htt: / ^, my ¾ doc-stoc ■■ Con ^ 'docs / 66038 6 / ProSim-lus-Ma ^ el # ■

Claims

A method of drying wet gas using desiccants and regenerating desiccants, comprising the steps of:

a) adsorption of the water contained in a wet gas by circulating it on at least one bed of desiccants,

b) regeneration of desiccants by circulating a synthesis gas on desiccants saturated at least partially so as to implement the so-called reaction reaction of gas to water (WGS acronym for "Water Shift Gas") between the water from saturated desiccants and carbon monoxide CO present in the synthesis gas.

2. Method according to claim 1, the desiccants being selected from an activated alumina, a zeolite, a silica gel, an activated carbon.

3. Method according to claim 2, step b / being carried out by an activated alumina impregnated with a catalyst.

4. Process according to claim 3, the catalyst being based on molybdenum sulphide (MoS), cobalt and molybdenum sulphide (CoMoS) or iron oxide.

5. Method according to one of the preceding claims, the steps a / and b / being carried out continuously or discontinuously.

6. Method according to claim 5, the steps a / and b / being carried out continuously by circulating the desiccants in the form of a fluidized bed.

7. The method of claim 6 in combination with claim 3 or 4, step b / being performed by circulating the fluidized bed desiccants on a fixed bed of catalyst.

8. Process according to any one of the preceding claims, the desiccants being in the form of beads.

9. Process according to any one of the preceding claims, step b / being carried out with a synthesis gas whose temperature is between 160 ° C. and

250 ° C, preferably at about 200 ° C.

10. Process according to any one of the preceding claims, according to which a cleaning step of the synthesis gas is carried out before or after step b /.

The process according to any one of the preceding claims, wherein prior to step a /, the desiccants are swept by circulating an inert gas, such as CO 2, nitrogen or other inert gas.

12. Process according to any one of the preceding claims, the synthesis gas of step b / being produced by reforming methane or by partial oxidation of methane or gasification of a charge of carbonaceous material.

13. Process according to any one of the preceding claims, the wet gas being either a natural gas or ambient air.

A method of thermochemically converting a feedstock of carbonaceous material into a synthesis gas to produce a fuel or fuel, such as a liquid fuel, or other synthetic product, comprising the steps of:

forcibly drying a carbonaceous material charge by means of the ambient air dried in accordance with step a / of the process according to any one of claims 1 to 13,

gasification of the feed in a gasification reactor (1), step b / of the process according to any one of claims 1 to 13, with the synthesis gas produced upstream by the gasification in the reactor.

15. Conversion process according to claim 14, wherein the load of carbonaceous material is lignocellulosic biomass.

16. Conversion process according to claim 14 or 15, wherein downstream of step b / is carried out a synthesis according to the Fischer-Tropsch process followed by hydrocracking to produce liquid fuel of the diesel or kerosene type.

17. Installation (1) continuously implementing the method (s) according to any one of the preceding claims, comprising:

- a first reactor (6) whose input is connected to a wet gas circuit,,

a second reactor (7) whose input is connected to a synthesis gas circuit,

circulating means (60, 70, 8, 9, 10, 11, 12, 13) for circulating circulating bed desiccants respectively inside the first reactor, from the first reactor to the second reactor and vice versa; versa, and inside the second reactor so as to implement the adsorption of the water contained in the wet gas in the first reactor, the regeneration of the desiccants by the synthesis gas on the desiccants at least partially saturated and the so-called WGS gas reaction reaction to water between the carbon monoxide present in the synthesis gas and the water present in desiccants in the second reactor.

18. Installation according to claim 17, wherein:

desiccants are in the form of beads,

the first (6) and second (7) reactors are arranged vertically, the circulation means inside the first reactor comprise guides (60) free of catalyst, fixed inside the first reactor, to allow the gravity circulation of the balls from the upper part of the first reactor in which they are unsaturated to the lower part of the first reactor in which they are saturated,

the circulation means of the first reactor to the second reactor comprise a first device (8) for fluidization of the balls, connected firstly to the first reactor and secondly to the second reactor via a pneumatic transfer line (9),

the circulation means inside the second reactor comprise guides (70) containing catalysts, fixed inside the second reactor, to allow the gravity circulation of the balls from the upper part of the second reactor in which they are saturated up to the lower part of the first reactor in which they are regenerated,

the circulation means of the second reactor to the first reactor comprise a second device (10) for fluidization of the balls, connected on the one hand to the second reactor and on the other hand to the first reactor by a pneumatic transfer line (11) comprising at least one pressurized transfer chamber (12) for storing the regenerated balls under pressure.