Classifications

• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F11/00—Treatment of sludge; Devices therefor
  • C02F11/06—Treatment of sludge; Devices therefor by oxidation
  • C02F11/08—Wet air oxidation
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F11/00—Treatment of sludge; Devices therefor
  • C02F11/06—Treatment of sludge; Devices therefor by oxidation
  • C02F11/08—Wet air oxidation
  • C02F11/086—Wet air oxidation in the supercritical state
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
  • C10K1/00—Purifying combustible gases containing carbon monoxide
  • C10K1/04—Purifying combustible gases containing carbon monoxide by cooling to condense non-gaseous materials
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0953—Gasifying agents
  • C10J2300/0956—Air or oxygen enriched air
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0983—Additives
  • C10J2300/0986—Catalysts
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/12—Heating the gasifier
  • C10J2300/1246—Heating the gasifier by external or indirect heating
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
  • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
  • C10J2300/1643—Conversion of synthesis gas to energy
  • C10J2300/1646—Conversion of synthesis gas to energy integrated with a fuel cell
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
  • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
  • C10J2300/1643—Conversion of synthesis gas to energy
  • C10J2300/165—Conversion of synthesis gas to energy integrated with a gas turbine or gas motor
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
  • C10J2300/1671—Integration of gasification processes with another plant or parts within the plant with the production of electricity
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
  • C10J2300/1807—Recycle loops, e.g. gas, solids, heating medium, water
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
  • C10J2300/1861—Heat exchange between at least two process streams
  • C10J2300/1884—Heat exchange between at least two process streams with one stream being synthesis gas

Definitions

• the present invention relates to a method of the thermal treatment of an aqueous fluid comprising carbonaceous material to be gasified, to yield a combustible gas.
• the gasification of carbonaceous material such as coal in the presence of steam and a limited amount of oxygen has been known in the field for some time. Due to the combustion of a portion of the coal in a suspension of coal in water, the suspension becomes very hot. As a result, at a temperature of 1000-1200°C and a pressure of approximately 50-100 atmospheres, a carbon monoxide- and hydrogen-comprising combustible gas is produced.
• the object of the present invention is to improve the known method and in particular its energy efficiency.
• An additional object according to the invention is to improve the control of the thermal treatment .
• the method according to the invention comprises the following steps: i) feeding the aqueous fluid comprising carbon- aceous material to be gasified to a reactor comprising a course of treatment; ii) transferring heat to the carbonaceous material- comprising aqueous fluid in counterflow; iii) the gasification of the carbonaceous material in the course of treatment at an elevated temperature in the presence of water, to yield a product stream comprising combustible gas and a carbonaceous material-depleted aqueous fluid; and iv) cooling the product stream until the carbona- ceous material -depleted aqueous fluid at least partially comprises a carbonaceous material-depleted aqueous fluid and the separation of the combustible gas from the carbonaceous material-depleted aqueous fluid.
• Step iii) is carried out under low-oxygen or anoxic conditions. More specifically, no oxygen is added. According to a preferred embodiment the gasification in step ii) is carried out at a temperature and pressure equal to or higher than the critical temperature and pressure of water.
• step iii) gasification occurs preferably at a temperature higher than 400°C, in particular at a tem- perature higher than 500°C.
• the product stream in step iv) is cooled by feeding it in counterflow to the aqueous fluid comprising carbonaceous material to be gasified.
• the temperature of the carbonaceous material-depleted aqueous fluid can be elevated in an energy-efficient fashion.
• the carbonaceous material-depleted aqueous fluid is heated, oxygen- comprising gas is introduced into the heated fluid, oxygen is reacted with the carbonaceous material present in the depleted aqueous fluid producing heat, which heat is transferred to an aqueous fluid comprising carbonaceous material to be gasified.
• oxygen is supplied to the carbonaceous material-depleted aqueous fluid.
• This causes carbonaceous material still present in the fluid to be combusted, yielding heat which is utilized to sustain the gasification process.
• the heat is released at a location where it can be transferred efficiently.
• Preheating the depleted fluid prior to the addition of oxygen provides an efficient manner of achieving a very high temperature. This is self-regulating. For instance, insufficient gasification of carbonaceous material at the onset means that more carbonaceous material is left over for oxidation, resulting in the elevation of the temperature, which in turn promotes gasification.
• the combustible gas is combusted in a combustion installation to yield electricity and heat.
• a por- tion of the combustible gas formed is used to attain the elevated temperature described in step ii) .
• This fuel is available on the spot .
• Subsequent heating is effectuated in particular by counterflow to the aqueous fluid comprising carbonaceous material to be gasified.
• the treatment of semi-liquid manure or manure by the method according to the invention means for one thing the utilization of its energy-content , and for another thing the resolution of problems regarding manure storage, environmental pollution and the spreading of disease.
• a first installation for the thermal treatment of an aqueous fluid comprising carbonaceous material to be gasified to yield a combustible gas and an aqueous fluid poor in carbonaceous material to be gasified comprises a high-pressure pump for feeding under high pressure the aqueous fluid comprising carbonaceous material to be gasified to an elongated tubular reactor having a first and a second end, wherein the first end is provided with an inlet for the aqueous fluid comprising carbonaceous material to be gasified, and the second end is provided with an outlet for the carbonaceous material-depleted aqueous fluid, which reactor is provided in a chamber of an incinerator, which chamber is separated from the lumen of the tubular reactor by means of a heat-conducting reactor wall defining a course of treatment, at the side of the outlet of the tubular reactor the incinerator is provided with a first inlet for oxygen-comprising gas and a second
• the hot combustion products can be used for the production of steam, and optionally of electricity. It is also possible to fire the incinerator under a pressure of, for instance, 20 bars. It is then possible to utilize the combustion products for the generation of electricity by means of a turbine. In such a case the incinerator is preferably fired utilizing the gas formed by the method under high pressure.
• the incinerator may be a fluid bed in which the bed material is, for instance, aluminium oxide. This pro- motes the transfer of heat to the reactor wall.
• the fuel may be gaseous, liquid or solid.
• the bed material may comprise a catalyst in order to, for instance, keep the nitrogen emissions low.
• the incinerator itself may be a reactor in which at high temperatures an exothermal conversion takes place, yielding a desired product.
• the preparation of such products may include, for instance, ethane or synthesis gas resulting from the partial oxidation of methane.
• the gas formed is worked up in a manner known in itself.
• source for methane worked up combustible gas obtained by the method according to the invention may be used.
• the installation comprises a heat exchanger conducting the carbon- aceous material-depleted fluid coming from the tubular reactor in counterflow to the aqueous fluid comprising carbonaceous material to be gasified.
• Such an installation is capable of gasifying carbonaceous material in a very energy-efficient manner.
• the installation comprises a heat exchanger for conducting combustion products coming from the incinerator in counterflow to oxygen-comprising gas to be supplied to the first inlet.
• the reactor can reach very high temperatures, so that virtually complete a conversion of carbonaceous material into gas is guaranteed.
• the very hot combustion gasses leaving the exhaust can be utilized for the production of steam, for instance for the generation of electricity.
• an alternative installation for the thermal treatment of an aqueous fluid comprising carbonaceous material to be gasified to yield a combustible gas and an aqueous fluid poor in carbonaceous material to be gasified comprises a gasification reactor having a substantially elongated first chamber and a substantially elongated second chamber, the first chamber comprising an inlet opening for the thermal treatment of aqueous fluid comprising carbonaceous material to be gasi- fied, the first chamber and the second chamber being separated by a heat-conducting wall, which heat-conducting wall defines a course of treatment along which, after separation of the combustible gas, the aqueous fluid comprising carbonaceous material to be gasified is conducted in counterflow to an aqueous fluid which, as a result of thermal treatment, has become poor in carbonaceous material to be gasified and has been separated from combustible gas
• the installation further comprises means for separating the combustible gas and the aqueous fluid which, as a result of
• Such an installation makes an energy-efficient, self-regulating thermal treatment of fluid comprising carbonaceous material to be gasified possible.
• the means for separating the combustible gas from the aqueous fluid which, as a result of thermal treatment, has become poor in carbonaceous material comprise a heat exchanger.
• the installation according to the invention comprises means for the combustion of the combustible gas, yielding electricity and heat.
• the installation further comprises a heat-conducting surface for transferring to at least one chamber heat released during combustion.
• the first chamber surrounds in the longitudinal direction substantially the second chamber and the heat-conducting surface surrounds in the longitudinal direction substantially the first chamber.
• FIG. 1 is a schematic illustration of a first installation suitable for carrying out the method in accordance with the invention
• FIG. 2 schematically illustrates a portion of a second installation suitable for carrying out the method in accordance with the invention.
• Fig. 3 is a schematic illustration of a third installation suitable for the application of the method according to the invention.
• a reactor 1 having an inlet 2 for a carbonaceous material- comprising aqueous fluid to be thermally treated.
• This fluid may be prepared in a vessel 3 into which water (H 2 0) and a carbonaceous material (C) are introduced.
• This carbonaceous material may be shredded biomass, coal, manure, etc.
• a pump 4 By means of a pump 4 a solution or suspension of the carbonaceous material-comprising aqueous fluid to be thermally treated is introduced into the reactor via the inlet 2.
• the inlet 2 debouches into an elongated first chamber 5 which is separated from a second chamber 7 by a heat-conducting wall 6.
• the carbonaceous material is gasified yielding a mixture of combustible gas and a carbonaceous material- depleted fluid.
• this mixture leaves the reactor 1 via outlet 8 and enters a heat exchanger 9, in which the mixture is cooled.
• This cooling process promotes the separation of combustible gas from carbonaceous material-depleted fluid.
• the depleted fluid is separated from the combustible gas.
• this combustible gas may be transported to an installation 12, which installation 12 is suitable for the generation of electricity.
• the installation 12 may comprise a turbine, a combustion engine or, in combination with a reformer for increasing the hydrogen content in the gas, a fuel cell.
• the carbonaceous material -depleted fluid from vessel 10 may be heated via the heat exchanger 9 and, with the aid of pump 13, introduced under increased pressure into the second chamber 7.
• an oxygen- comprising gas such as preferably air
• the oxygen reacts with carbonaceous material still present in the depleted fluid, yielding heat.
• this heat is transferred to the aqueous fluid comprising carbonaceous material to be gasified. It is preferred that in the second chamber near the inlet 15 super critical conditions prevail to allow ready and homogenous mixing of oxygen and carbonaceous material-depleted fluid.
• the fact that the energy necessary for gasification is provided by oxidation of the remaining carbonaceous material, affords a highly self -regulatory thermal treatment process.
• the cooled, essentially carbonaceous material- free fluid leaves the reactor 1 via outlet 16 and flows, in the embodiment shown, into a vessel 17 to separate clean water 18, that may be discharged or used for the preparation of a carbonaceous material -containing aqueous fluid, from inert gasses such as carbon dioxide and possibly nitrogen gas formed during oxidation.
• the carbonaceous material-comprising aqueous fluid to be thermally treated comprises a catalyst to promote the formation of combustible gas.
• This catalyst may be an ion or a precious metal particle which, if the clean water from vessel 17 is to be reused for the preparation of suspension, may be allowed to go through the cycle once or several times more, until the clean water contains too many anorganic salts originating from the carbonaceous starting material so that part of, or all the water has to be discharged or improved.
• the installation according to the invention may also comprise means (not shown) for the utilization of the pressure energy.
• This may be utilized for the generation of energy or to aid in returning the carbonaceous material-depleted liquid to the reactor 1, more specifically to its second chamber 7.
• the pressure energy from the gas leaving the vessel 10 it is, for example, possible to utilize the pressure energy from the gas leaving the vessel 10.
• the pressure energy from the liquid leaving the vessel 17 may also be utilized to relieve the pump 4 or for the generation of electricity.
• FIG. 2 An alternative embodiment of an installation according to the invention is schematically illustrated in Fig. 2.
• the mixture described above After the mixture described above has left outlet 8, it is cooled in heat exchanger 9.
• the heat energy being released is utilized for heating the carbonaceous material-comprising aqueous liquid to be thermally treated in heat exchanger 9' .
• heat exchanger 9 and 9' are one and the same heat exchanger.
• the cooled mixture, being highly compressed, may be allowed to expand over a turbine 19 to generate electrical energy.
• an oxygen-comprising gas usually air, the gas may then be combusted. This may be done in a second turbine 20, producing heat and electricity.
• the still hot combustion gasses from turbine 20 are utilized in a heat exchanger, for in counterflow heating of carbon-depleted liquid from vessel 10. With the aid of a pump 22, this liquid is transported to the second chamber 7. Between the vessel 10 and the turbine 19 a heat exchanger 23 may be placed, for heating combustible gas from the vessel 10, which allows a further increase of the pressure and consequently of the performance of turbine 19.
• the necessary heat is preferably supplied by the stream leaving the second chamber 7 via heat exchanger 23', which is preferably one and the same as heat exchanger 23.
• the com- bustion gasses may also be supplied to a further installation for the thermal treatment of a liquid, such as a liquid comprising carbonaceous material to be gasified, which installation possesses a heat-exchanging partition between a first and a second chamber, as well as a heat- exchanging surface for transferring heat from combustion gas to colder liquid.
• a liquid such as a liquid comprising carbonaceous material to be gasified
• the supply of oxygen is omitted if the gasification takes place at a temperature and a pressure well above the critical temperature and pressure of water.
• an installation of the kind illustrated in Fig. 3 may be used which has a capacity of 100 MW relating to the energy contents of the carbonaceous material.
• the installation com- prises a high-pressure pump 24 by means of which a sludge
• a of shredded biomass such as wood flour having a solid content of 20%, is transported at a pressure of 30 MPa, via a heat exchanger 25 and an inlet 26 into a tubular reactor 27.
• the tubular reactor 27 is suitably made of Incoloy 625 and has a (total) length of, for example, 725 m and a surface area of 114 m 2 .
• the carbonaceous material-depleted stream leaving the reactor 27 via outlet 28 is led through the heat exchanger 25 in counterflow to the sludge A and is optionally cooled further to a tem- perature of 25 °C, for example by using cooling water in heat exchanger 29.
• the combustible gas formed in the reactor 27 is separated from the carbonaceous material- depleted stream by means of a gas/liquid separator 30.
• a gas/liquid separator 30 By lowering the pressure above said depleted stream to, for example, atmospheric pressure, it is possible to recover more gas from the depleted stream which may be used, for example, for heating the sludge A to be gasified further.
• the prevailing high pressure makes it advantageous to use a membrane for the separation of hydrogen from the stream.
• the remaining gas stream may be fed to an incinerator 32 having a height of 10-15 m, in which the reactor 27 is provided.
• the incinerator 32 also comprises an inlet 33 for an oxygen-comprising fuel such as air. As shown in Fig.
• the sludge to be gasified is led in counterflow to the hot gasses released during combustion.
• the hot gasses leave the incinerator 32 via an exhaust 34 and their energy contents are used for heating air which is to be supplied to the incin- erator 32 via inlet 33, by counter-flowing the hot gasses to the air in the heat exchanger 35.
• a suitable installation is provided with, for example, a heat exchanger 25 having a surface area of 888 m 2 and a heat transfer coefficient of 1200 W/m 2 .K and is fed at a rate of 32 kg dry matter (in 128 kg water) per second.
• abstaining from the use of oxygen-comprising air results in the combustible gas having only a low nitrogen content. Partly for that reason, the gas has a high caloric value so that it can be applied more generally.
• the temperature required for the gasification of the carbonaceous material can be determined quite easily by a person skilled in the art.
• the solid content is suitably at least 10% and preferably at least 20%, such as at least 30%.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Combustion & Propulsion (AREA)
• Environmental & Geological Engineering (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Life Sciences & Earth Sciences (AREA)
• Hydrology & Water Resources (AREA)
• Water Supply & Treatment (AREA)
• General Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Industrial Gases (AREA)
• Treatment Of Sludge (AREA)

Applications Claiming Priority (3)

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• 1997
  • 1997-06-26 NL NL1006404A patent/NL1006404C2/nl not_active IP Right Cessation
• 1998
  • 1998-06-26 WO PCT/NL1998/000371 patent/WO1999000334A1/en not_active Application Discontinuation
  • 1998-06-26 EP EP98931143A patent/EP0991597A1/de not_active Withdrawn

Non-Patent Citations (1)

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