WO2005045204A1

WO2005045204A1 - Method and arrangement for recovering energy and chemicals

Info

Publication number: WO2005045204A1
Application number: PCT/SE2004/001465
Authority: WO
Inventors: Bengt Henry Nilsson
Original assignee: Ultirec
Priority date: 2003-10-15
Filing date: 2004-10-13
Publication date: 2005-05-19
Also published as: WO2005045204A9; SE0302718D0; SE526905C2; SE0302718L

Abstract

The present invention relates to a process for recovering energy and chemicals from a fuel comprising a part or parts of: hydrogen, hydrocarbon and hydrogen compounds by combustion/thermal decomposition during partial and/or total oxidation, in at least one reaction chamber during at least one reaction progress above atmospheric pressure after which produced gas, superheated or during partial or total moisture saturation, with the content of chemical and/or physical energy to be cleaned during the condensation of vaporized agents and compounds during the expansion cooling by at least one expansion turbine step of at least one partial step when from the fuel oxidation progress originating gas carried sub-/microscopic and visual dust particles are wetted by condensation, which condensation preferably comprises steam when appropriate also by other condensable agents and compounds as volatilizable metals/heavy metals as well as volatilizable hydrocarbons, when said dust particles constitute condensation nuclei during the condensation, whereby the weight of said dust particles is increased whereupon said dust particles are transferred from the gas phase to the liquid phase, which phases are separated by at least one separation device, simultaneously when the gas phase contains chemical energy, said energy is utilized for production of chemicals and/or energy, while the physical energy during the expansion cooling is converted into power by an expander turbine connected generator, or used for driving a stationary machine/engine or a mobile machine/engine, while further chemicals are recovered as a phase of solid and/or molten material and/or said sub-/microscopic and visual dust particles and/or in aqueous form and/or in gaseous state.

Description

METHOD AND ARRANGEMENT FOR RECOVERING ENERGY AND CHEMICALS

STATE OF THE ART AND PROBLEMS

At all kinds of combustion regarding energy production there arc a number of efficiency restraining areas on the heat exchangers which, will lower the efficiency of the energy production. The convertible part of the energy is indicated as exergy and the non convertible part is indicated as anergy. The following relationship thus prevails: Energy = Exergy + Anergy. Therefore the aim must he to do not "destroy³⁷ high quality exergy by converting it to inapplicable energy —that is anergy. Many of the established energy recovery processes have great exergy losses. An indication of this is large cooling wateT consumption with the corresponding amount of waste heat Combined power and heating plants are more and more used for energy production from hydrocarbon compounds in the form of as well renewable fuels as fuels of fossil background The combined power and heating plants generate both electric current/power and a great part of Mgh-terπperature hot water - the latter nnfortαnately at least 2/3 of the total energy amount. The requirement is therefore a well built out district heating system which by that constitutes the utmost production limit for the combined power and heating plant. The global energy situation is precarious in view of increasingly high set environmental requirements- Fuels of fossil background must be avoided and in the long run completely eliminated, as these are a limited resource, and to reduce/emninate the emission of fossil carbon dioxide. Also emissions to a much larger extent of green-house supported gases of nitrogen dioxide and volatile organic agents and compounds, as well for allergy, asthma, cancer as for lung diseases and for heart and blood-vessels unhealthy iπhalational dust particles must immediately be reduced radically and eliminated in the long run. Furthermore, in many countries forces are at work to carry through a nuclear phase-out By that there only remains a future cychiig revolution adapted society based on renewable energy sources - i.e. revolution fuels. Here the bio energy ]has a very advanced place. However, increased bio energy utilization takes place in powerful competition with other interested parties as the established pulp and saw mill industry. The pulping industries of the world together handle a gigantic amount of renewable energy in the form of biomass as raw material for pulp production. De f-J lng on

trrthod and tvpe of paper products, the real part of used biomass for paper production is only about 45-55 %.. The remaining part of the biomass — thus about half the amount— constitutes a high-quality liquid bio fuel mixed with the chemical contents of the waste liquors. Besides, these liquors contain m most cases alkali compounds which have a catalysing and positive effect on the combustion progress. The recovery potential of bio energy in the pulp mills coincides well with the global need of increased utilisation of revolution based energy. The great possibility is grounded on the fact that the handling of the raw material/bio energy is already established as well as the re-growth of the biomass itself is secured Further investments regarding pulp production in order to make possible an increased utilization of unchanged amount of bio energy are thus not necessary. On the other hand, there is a need for a completely new procedure for energy recovering from the available bio fuel with the intention of reducing the exergy losses and above all of giving priority to the efficiency of (electric) power generation. The need also comprises the emission situation to the air and water — i. e. the environmental aspect. The ultimate pulp mill must be seen from an overall perspective as a natural part in a well balanced ecological process with integrated partial processes, where the energy excess of the pulp mill essentially is used for power generation. Power producers all over the world are mobilizing enormous resources to find technical solutions for handling generated fossil carbon dioxide and by that, during a transitional period, make continuous combustion of these fossil fuels possible. Fossil fuels will most probably dominate the world during additionally two, three generations. This handling of carbon dioxide means that the gas is separated from flue gas and compressed to condensation (liquefied) to be utilized within different markets. An alternative which has grown stronger during the last years means storage/final waste disposal of liquefied carbon dioxide in a suitable ground, for example porous sandstone, very deep or in emptied oil wells, natural gas fields etc. It has not yet been worked out any well functioning method for the recovery/separation, of carbon dioxide with consideration to environment and economy - the latter prmcipally regarding avanab-lity. energy efficiency and in small scale. Regarding the present energy balance of resources in many countries there often exist imbalance and depends on the supply of a couple of the energy types: fossil fuels, nuclear power, water- power and bio fuels. Thus, too often "a third leg" is missing in order to give necessary stability to the energy balance. This stabilizing '"third leg" could be composed of bio fuel supply by the pulping industry where this is possible and. for the time being of the handling/taking care of the carbon dioxide of the fossil fuels. The environmental aspect is also about the need of some form of mini power stations and the constantly growing transport

miui powsr ^•stataorrs.-'among --σ crs

town, with possibility to adjust the distribution between produced (electric) power and heat according to the needs and/or the time of the year. The possibilities of the transport sector to a radical change of the emission situation are perhaps the utmost greatest environmental problem. The technological development for as well combined power and heating plants as the transport sector has ceased. The respective technological area has during a long time been refined and optimized, but now a great technological leap is needed The recovery technology of the pulping industry has by tradition been most concentrated on getting back the cooking chemicals and secondly to produce steam for the pulping process with a certain excess as high pressure steam for (electric) power - henceforward in the present invention only named power - generation by generators connected to steam turbines. The digester waste Hquor content of dissolved organic substance is also used as a fuel for conversion/thermal decomposition of recovered digester chemicals in a so called Tomtinson- boiler - most often called recovery boiler. At present, this constitutes the heart in the recovery system of the pulping industry and is the most expensive unit in the pulping production line. The recovery boiler was introduced already during the rnneteen-tbirties and is very sensitive for disturbances from operation-, maintenance — and safety point of view. The boiler is completely static from chemical recovery point of view and does not in any way fulfil the present process requirements of the deHgnification process - among others the requirements of cooking with optimized sulphidity profile and the recovery of sulphide free alkali —mainly for bleaching. The recovery system will therefore be the key to the control of the chemical balance of the pulp mills with direction on separating the sodium-/potassium compounds from the sulphur compounds and to eject/separate none process elements ( PE), comprising all forms of metals and chlorides out of the chemical cycle. From capacity point of view there is a process requirement on high content of dry solids (DS) of the waste liquor going to the recovery boiler. The flue gas from the boiler brings a great quantity of ∑ilkaline dust particles as sub-/microscopic and visual particles, so called fly ash, which in spite of installation of expensive systems in the form of electrical filters and gas scrubbers more or less continuously blow out a partial flow of this dust Traditionally, the pulping processes embody very large exergy losses and are therefore consumers of huge amounts of cooling water with the corresponding generation of more or less low-grade warm water. Considerable steam users are the evaporation apparatus/effects before the recovery boiler. Here for example the released black hquor of DS-percentage 15-17 % from the sulphate pulp digester is evaporated and via the mixed-base Hquor/interrnediate liquor concentration further evaporated to heavy black

the DS-percentage up to the level of 85-S7 % with the corresponding increased consumption of intermediate pressure steam, Th& effects/heat exchangers of the evaporation have the tendency at higher DS-percentage to obtain coverings, mcrusts/fouling that are difficult to dissolve, on the liquor side of the heat exchangers and must be shut down and washed regularly. At DS-ρercentages above the area 45-55 %, the solubility of the black liquor content of among others sodium carbonate (Na₂CO3) and sodium sulphate (Na SO<t) is reduced which tends to precipitate- Further the heavy black liquor with an increased DS- percentage obtains an exponential increase of the viscosity - already pronounced over DS- percentage around 65 % - and is by that difficult to handle. An extra black liquor pre treatment stage during increased temperature needs to be installed in order to decrease the viscosity. The installation is expensive and further increases the corisurnption of valuable intermediate high pressure steam. The evaporation is a gradual process, from overpressure down to negative pressure/vacuum, where mixed-base Hquor/intermediate liquor is stored in big tanks for separation of the light floating sulphate soap. The separation constitutes a condition of the continued evaporation up to DS-percentages above the intermediate liquor DS-area in order to prevent formation of foam and minimize the coating as fouling/incrusts on the liquor side of the heat surfaces. Separated soap has a certain market value and is offered for sale for external further treatment and/or is used within the mill as a fuel. In most cases, the soap handling is not economically defensible but principally constitutes a process demand for the continued DS-increase of the black liquor. The possibility of a modern (read autumn 2003) recovery boiler for recovering energy during combustion of black hquor is distributed as follows: • Power 12 % • Steam production 54 % • Energy losses 34 %

As can be seen from above, the recovery boiler process comprises a great part of exergy losses.

The latest attempts of development within the recovery area have been black hquor gasification. Studies were made already at the end of the n eteen-fifties. There are two different kinds of gasification processes, low temperature gasification and high temperature/ melt gasification. When using the low temperature gasification, below melting point 760 - 800°C, this results in the recovery of chemicals in the form of sodium carbonate fN ₂CO₃) as a solid phase and a fuel gas containing sulphur as hydrogen sulphide (H₂S). Low temperature

of formed sodium sulphide fNa₂S) as a melt phase and insufficient carbon conversion which together require a complicated after-treatment. The other gasification process, the melting process, with a theoretical melting temperature above S00°C but according to experiences with a necessary reaction temperature during the gasification within the temperature interval 960 - 1100°C The melt fraction contains both of sodium carbonate (Na₂CO₃), some sodium hydroxide (NaOH) and sodium sulphide (Na₂S) with the remaining amount of sulphur as hydrogen sulphide (H₂S) into the fuel gas. The engineering company, Kamyr AB, Karlstad, Sweden began in 1989 to introduce the so -called "Chemrec-booster"- concept, -which is a melting^rocess. This -concept resulted in two ' installations with the intention of only increasing the capacity of the chemical recovery. The concept is static regarding recovery of chemicals and has even inferior energy recovery than the recovery boiler. Both the installations gave the experiences, regarding the required temperature level of the gasification process, that temperatures above 900°C there is gaseous alkali in considerable quantities in the form of monatomic soάium/potassium (Na/K) and sodium hydroxide/potassium hydroxide (NaOH OH) with presence in about equal parts. These are increasing in quantity exponentially with the temperature increase above 900^σC. The reaction place for this gaseous alkali is in the main during the begmning of the reaction progress. Very serious chemical attacks on the interior ceramic lining of the reactor - essentially the upper 1/3 part - indicate this. Further an experience of increased temperature level during the reaction progress is the increased viscosity of the gas compounds. By this the in mixing of oxidants is more difficult, with the following res »trictions in the diffusion controlled reaction progress, owing to the occurrence of reaction retarding laminar boundary layers. Gases of high viscosity also mean formation of efficiency retarding strake formation/stagnant zones in the reaction vessel, which to a great extent shorten the very sensible, real retention time for the reaction progress. A pressurized concept was launched by Kamyr AB during the early nineteen-nineties and was based on so called "combi-'Vcombined cycle — integrated gasification combined cycle (IGCC). This combi concept comprises as well gas turbine as steam turbine, both with adherent electric generators- The expectations were by this to double the power generation in comparison with the established recovery boiler process. The combi concept can be seen in the patent documents SE-C-44S 173 and US 4.808.264. The combi concept claims to a still more extent than the recovery boiler black hquor of the highest possible DS-content in order to obtain fuel gas of a sufficiently high heat value, thus a great amount of chemical energy for

compressed air as oxidizing agent for the reaction progress this implies that a great amount of inert nitrogen must be compressed and heated up to the reaction temperature. The fuel gas is by this a typical low-quality gas which is not adjusted to standard gas turbines- This will limit the turbine selection and by that the costs and the complication degree will be increased to a great extent for the combi concept The concept therefore requires oxygen as oxidizing agent which means investments in expensive and energy demanding separation plant. In cornTor ity with most of the systems for energy production also the combi concept has inconvenient exergy losses with <κ>ιτespondϊαg cooling water need and production of waste water. The split of sodium- and sulphur compounds between the melt and gas phase, which is so important for the deligmfication partial processes, is limited- At all combustion of waste liquors from the pulping industry during partial oxidation, thus understoichiometric combustion, the distribution of the fuel gas content between chemical and physical energy is quite decisive for the continued energy recovery. At an operation example with black liquor of DS-content 73 %, oxygen 95 %, reaction temperature 950°C, reaction pressure 32 bar (a) the part of physical energy, latent and sensible heat, of the fuel gas is about 37 %. By that the part of chemical energy will be sufficient for combustion in the combustion chamber of the gas turbine - effective heat value 8.303 kJ/Nm³ dry gas. At a similar operation example but with black Hquor of lower DS-content 43 %, rhus a more water content, the part of physical energy in the fuel gas increases to around 73 %. By that the part of chemical energy in the fuel gas will be too low for the combustion chamber of the gas turbine — effective heat value 3.733 kJ/Nm³ dry gas. During black liquor gasification the operation criteria of the reaction progress axe thus quite decisive for the recovery of as well chemicals as energy. Black liquor of high DS- content and the subsequent high viscosity results in restrictions in the burner system of the reaction vessel gasifier. These restrictions comprise the drop formation ability, mainly the possibility of small droplets formation and the very sensible drop size distribution. Further restrictions are the tendency of plug formation in the narrow, very sensible, channels of the burner spray nozzle. Black Hquor of high DS-content/viscosity, often with content of detached incrusts, creates troublesome erosion In the carefully dimensioned channels of the burner spray nozzle. The restrictions in the burner system impair direct the so called carbon conversion degree. This constitutes one of the most essential control parameters of the reaction progress and is a measure of the amount of remaining, un-bumt carbon — thus the amount of soot and hydrocarbon compounds. The carbon conversion degree must exceed 99,5 %. Restrictions in the burner system must not be compensated by increased operational

Increased operational temperature increases thus among others the alkali steam partial pressure of sodium and potassium compounds exponentially, which is devastating for the ceramic interior lining of the reactor or cooling tubes depending on type of reaction vessel/gasifier. The outgoing fuel gas contains un-burnt hydrocarbon compounds as well as sub-/ microscopic and visual dust particles of heavier hydrocarbons (tars) and of alkali compounds. The part of alkaline dust particles increases with lower oxygen/fuel ratio - thus with black liquor of higher DS-content The amount of these alkaline dust particles is about 10 — 20 % of the incoming alkali amount of the supplied black Hquor. The dust particles are ^racticahyimpossible to filtraterThere^re dustparticles in size^'sub microscopic 0,01 - 0,20 μ, thus as particle size corresponding to tobacco-smoke - but also exists in size microscopic up to 20μ and above as visual. The gas turbine has requirements, which are set very high, regarding the cleanness of the fuel gas. The sensible light metal blades do not permit heavier hydrocarbons in the form of sticky tar particles, and concerning the alkaH content the røa?άmurn permission by the gas turbine deliverer is only 1-10 ppb. A gas turbine based concept therefore requires extensive/expensive investments for eliπnnation of the particular pollutions of the fuel gas. The gas turbine is also expensive, complicated and sensitive to load variations with the accompanying low efficiency owing to inferior performance of the turbine at partial load One of the big advantages of the black liquor gasification vs. the recovery boiler is however the possibility, to a certain extent to separate/spHt sodium and sulphur compounds between the melt and the gas phases during the reaction progress. The requirements of the gas turbine concept for black Hquor of a high DS-content and for the gas turbine adjusted pressure of the preceding reaction process, mean however that the adaptabihfy of the concept to fibre process requirements will be limited. This happens as the equilibrium reactions during the reaction progress in practice will be quite static. The calculated energy recovery of the combi concept at partial combustion of black liquor in reaction vessel is distributed as follows: * Power 21 % * Steam production 50 % « Energy losses 29 % ^"When comparing with the estabHshed recovery boiler process the production of power is thus calculated to be about 75 % higher. Also the combi concept has as can be seen relatively great exergy losses. The appHcation of black Hquor of the co bϊ concept has not yet left the concept stage and there is a certain hesitation witliin the pulping business — principally regarding the availability but also tbe complexity and the costs. Pressurized gasification of black Hquor is unique in comparison with apparently similar processes and fuels. At present there are a number of process criteria, which are incompatible when trying to totally op1_bmize the black Hquor gasification. This recovery process therefore requires a totaUy new process design, an overall view, to avoid known difficulties and at the same time try to fulfil the process requirements of the delignification process and to make integration advantages with connected processes possible, for example black Hquor evaporation with adherent partial processes. The pulping process including the recovery of chemicals and energy must be seen from a crosswise scientifically, overall perspective in order-to achieve the possible synergetic effects. The ultimate recovery forms the central axis around which the whole pulping process rotates comprising delignification, environmental considerations, energy recovery from a Hquid bio fuel and furthermore economy in the form of essentially power generation and operation availability with the possmiHty to design small scale plants. The foUowing description of the present invention is exemplified by method and arrangement for recovering different forms of energy, and when appropriate also chemicals, from different types of fuels cluding different amounts of water, thus different steam partial pressures during the reaction progress in the reaction chamber with most of the exempHfications made by the many waste Hquors of the pulping industry comprising as well sulphate pulp processes as occurring sulphite pulp processes of different basal chemistry - bases as sodium (Na), magnesium (Mg), ammonium (NH ) and also calcium (Ca).

To conclude it is most encouraging, with regard to the variety of the present invention and the global energy situation that owing to the accelerating greenhouse problems, to state that for example in a modern pulping industry., from wood raw materia bio mass point of view, there is a potential to a four- or fivefold increase of the (electric) power recovery/generation. The comparison is made with the estabHshed recovery technology of today during an unchanged amount of supplied wood raw material.

BRIEF, GENERAL DESCRIPTION OF THE INVENTION

The present invention offers method and arrangement for recovering energy and when appropriate also chemicals, recovering chemicals mcluding part or parts of: solid and/or molten material, sub- microscoρic and visual dust particles, in sohd and/or aqueous form and/or gaseous state, from a fuel comprising a part or parts of: hydrogen, hydrocarbons and hydrogen compounds, by combustion thermal decomposition during partial and/ot total oxidation in at least one reaction chamber during at least one reaction progress above atmospheric pressure whereupon produced gas, superheated or during partial or total moisture saturation, with content of chemical and/or physical energy is cooled and cleaned during condensation of into the gas vaporized agents and or compounds, by expansion cooling through at least one expansion turbine during at least one partial step, when from the oxidation progress originating gas carried sub-/microscoρic and visual dust particles, of sizes from around 0,0 Iμ are wetted by being condensation nuclei during the condensation, which ^"comprises as^'Well (water-) ^"steam as vol^'atileτjrgarHc-agents and compounds and volatile metals, when the weight of the dust particles increases and said particles are transferred from gas phase to Hquid condensale phase, which phases are separated by a separation device, simultaneously the content of physical energy during the expansion cooling is converted to power via a generator connected to the expander turbine, alternatively a turbine connection for operation of a stationary or mobile engine/vehicle - the latter on land, at sea or into the air. The partial pressure of the steam during the reaction progress is at least equivalent to the oxidation equivalence of the incoming hydrogen, which preferably is increased by water additives with the incoming fuel, external condensate, returned condensate, oxidizing agent and or steam additive direct into the reaction chamber, whereby the part of physical energy of the gas is increased correspondingly at the cost of the part of chemical energy. Water and or steam can also be added to the gas phase after the reaction progress for partial or total moisture saturation at the present pressure. The water additive is most suitably composed by separated condensate after expansion cooling and is preferred to condensate from the first expansion cooling stage. When multi stage expansion cooling, with return of hot condensate, makes segregated condensate recovery possible with reference to as weH flow_ pressure, temperature and cleanness with the energy recovery during very high total isentropic efficiency. A preferred performance is made by the comparatively high steam partial pressure (H₂O) during the reaction progress, which steam besides available oxygen (O₂) and carbon dioxide (CO₂), strengthen the oxidation potential of the progress. The steam reduces the partial pressure of the hydrocarbons and favours above all the final oxidation of the remaining hydrocarbon compounds during ϋx& final phase of the reaction process - some kind of steam reforming. Steam is in this respect 3 —4 times as efficient as for example carbon dioxide. When using fuels containing sulphur and alkaH compounds the increased water content/steam during the oxidation progress has also a dramatic effect on the sulphur separation, which at

gas combustion as s dphπτ dioxide (SO2). The increased water content also reduces the flame top temperatures during the reaction progress whereby the origin of thermal nitric oxide (NOχ) is radicaUy reduced As weH fuel as air related nitrogen are thus counteracted to form nitric oxides and already formed nitric oxides can furthermore be converted to nitrogen gas (N_D and steam by the injection of ammonia (NH3) or urea ( H₂)₂CO into the flue gas. The . extraordinary high water evaporation enthalpy makes the evaporation to a very energy requiring process by the presence of hydrogen bindings which connect the molecules. The water is therefore in this respect unique and more like a solid material than other liquids. The evaporatiomof the -water during -the initial reaction progress is -by that-a heavy physical energy absorption, endothermic reaction, at the expense of the chemical energy part of the gas phase with the corresponding addition of the physical energy part of the gas phase — thus addition of the sensible and latent heat content of the gas. The water thus constitutes a most natural and effective energy carrier, acting direct between the sequences evaporation/energy reception and condensation/energy delivering without any efficiency restrictive influence on heat exchanger surfaces. By this an energy conversion, harmless to the environrnent during ntinimum of exergy losses, in the form of generated power or expander turbine connected transmission for operation of stationary or mobile machine is obtained. When appropriate, from the oxidation progress originating soHd phase of some type of slag, melt heavy metals and chemicals, this phase is separated after the reaction progress in a melt cooler/dissolver (so called quench) by water containing additives, preferable returned condensate. When operating case with a suitable gas amount for recovery from the gas phase, for example a sulphur compound, this is made by some form of selective proceeding, by means of for example alkaH for H₂S and SO₂, within the suitable pressure and temperature area during and/or after the expansion cooling. When understoichiometric combustion of sulphur rich fuels takes place, the selective recovery of hydrogen sulphide (H₂S) is made possible, whereupon the H₂S constitutes a raw material for a diversified preparation of a number of chemicals. When presence of remaining chemical energy in the gas phase, this gas is fuhy combusted in another/second reaction chamber within the expansion cooling sequence or fuhy combusted in a gas boiler or correspondingly, when appropriate with subsequent alternative recovery of suitable amount of gas - for example sulphur dioxide (SO₂)- It is possible to use flue gas condensation for preheating of suitable media, whereby the discharge gas, at the absence of air as oxidizing agent hi principle contains only carbon dioxide (CO₂) - suitable for recovery/utilization by being liquefied for other markets or long time storing/final waste disposal. The gas combustion can be supported

chamber or gas boiler, the latter used for preheating of the fuel for the reaction progress, oxidizing agent and heating of gas and or Kquid phase in connection with the expansion cooling process - everything to increase the physical energy level of the system — or for customary steam production with or without a steam turbine with adherent generator for power generation. The principal characteristics of the present invention and the direct key function are thus the conditions possibiHties around the high water steam partial pressure during the reaction progress comprising as weH process chemistry as the energy recovery. The appHcation of the present invention within among others the combined power and heating ^" ρlants^~and-the chemical^"and^~energyτecovery-of Hquors-witli 'the-pulping industry forms a sharp contrast to the technology state of the art and is a substantial breakthrough — a great technique leap. Principal diagrams according to figures 1 and 2 describe the present invention in a comprehensive form, with condensate recirculation, as some form of "energy pinwheel". In general there are no necessary transport pumps shown in any of the subsequent figures. -

DETAILED DESCRIPTION OF THE INVENTION

Figure 1: Dry fuel 30 is added to an internal, recycling condensate flow 32 with reaction progress in the reaction chamber 1 during total oxidation by alternative oxidizing agents.

Figure 2;

Water containing fuel 31/30 is added to an internal, recycling condensate flow 32 - forming a part of the total amount of condensate — with reaction progress in a reaction chamber 1 during partial oxidation by alternative oxidizing agents and terminal combustion of produced fuel gas. ha general, the apparatus and piping of these both figures constitute in appHcable parts of reaction chamber 1, expansion cooling turbine 2 with energy recovery in the form of generated power 20 via generator 3 and or power transmission, mechanical or hydraulic, for operation of stationary S or mobile engine 83 A, separation device for gas/condensate 14, secondary combustion chamber of fuel gas by gas boiler 12 with the possibility of heating recycling condensate and/or gas before the turbine expander and production of steam 89 via feed water 88, dry fuel 30, fuel carried water 31, to reaction chamber recycling condensate 32, expansion cooled clean condensate excess 34, gas before expander 38, gas after expander 39.

consisting of carbon dioxide (CO₂) and steam possibly with the contribution of inert nitrogen (N₂) originating from the fuel ox air additives. When operation case according to figure 1 comprising a dry fuel 30, in the form of gaseous hydrocarbon compounds, at total oxidation with stoichiometric combustion the temperature level around 1800°C is obtained with air 35 as an oxidizing agent and just above 3000°C with oxygen 36 as an oxidizing agent which temperature levels are reduced in relation to the amount of added water/recycling condensate 32 by the endomerrmc vaporization work, which is recovered during the condensation in the ' expansion turbine-stage 2 ήϊthe form^" of power 20-and/or mechanical or hydraulic operation of stationary or moHle machine during an absolute minimum of exergy losses. During the reaction/oxidation progress also an amount of steam equivalent with the hydrogen content of the fuel is formed, and this strengthens the steam partial pressure and ihe physical energy level of the gas. When air is used as an oxidizing agent a small moisture amount is also added in this way to "the reaction progress.

Figure 3: The principle for the progress of the expansion cooling and energy recovering by means of expander turbine can be seen of the enthalpy/entropy diagram (TS diagram) according to present figure.

The subsequent operation examples, figures 4 -25, illustrate the variety of the present invention but are not meant to limit its extent but can be varied or combined within the scope of the patent claims. Below can be seen process diagrams/figures 4 and 5 of more common direction.

Figure 4: Dry fuel 30 and recycling condensate 32 and turbo compressed air 35 as oxidizing agent are added to the reaction progress during total oxidation. From the reaction chamber 1 outgoing pressurized flue gas, superheated or during partial or total moisture saturation, connects via piping 38 the expansion cooling turbine 2 connected with turbo compressor 8 and the generator 3 for power generation 20 alternatively with common power transmission in the form of mechanical or hydraulic device for operation of stationary or mobile machine 83 A — the later for some form of transport/vehicle. From the expansion cooling turbine outgoing gas "^■ nd co Me i_-*^i-rI- .i-fe^^ ill6'^"Sii Hia^3Jort S7ice-l' iux-α^ldisg in gas fltro^ ■sSHfi&.i condensate flow 32. The outief counter-pressure of the expansion cooling turbine settles the temperature of the gas/condensate mixture with outlet pressure preferably lower than atmospheric pressure, thus a negative pressure/vacuum. According to this figure processes around atmospheric pressure are aimed at Heavy metals, non process elements (NPE), soot ashes and slag origmating from the reaction progress are separated by means of separation device 18. The recycling condensate flow 32 contains eariier vaporized water, volatile organic substances and compounds, volatile metals heavy metals (NPE) and earlier gas carried sub-/microscopic and visual dust particles, which dust particles are wetted during the "condeisation'progress" of the "expansion" cooling by forrning-condensation-nuclel whereupon the dust particles get heavier and are transferred to Hquid phase 32, with return to the reaction chamber 1 via the incoming fuel and for moistening of outgoing flue gas 38 and a small flow for the cooling and separation device for sohd phase 18. This smaU condensate flow prevents simultaneous bunding up of NPE in the system. The gas flow 44 thereafter connects suitable apparatus for recovery of the remaining, siuaH heat content of the flue gas by for example flue gas condensation 22 with subsequent alternatively placed eariier, fan 13 with flue gas outlet 45. The flue gas discharge 45 is composed by in principle only carbon dioxide (CO₂), which can be utilized by compression and condensation — Hquefying pressure 76 bar — nd utilized on various markets or as a final waste disposal down in suitable ground - for example in aquifers. If carbon dioxide in principle is required without any content of nitrogen/nitrogen compounds, compressed air 35 is suitably replaced by oxygen 36.

Figure 5:

The figure corresponds as a principle to the preceding figure 4, however with the exception that the fuel contains water and the procedure comprising expansion cooling in three stages- Fuel 30 with water content 31 and recycling condensate 32 and 33 with turbo compressed air 35 as oxidizing agent are added to the reaction chamber 1 for reaction progress during total or partial oxidation- Alternative oxidizing agents or in combination with each other are used, as oxygen (O₂) 36 and/or a hydrogen peroxide solution (H₂O₂) 37. From reaction chamber 1 outgoing gas, superheated or during partial or total moisture saturation, connects by piping 38 the expansion cooling turbine 2 connected to turbo compressor 8 and generator 3 for power generation 20. The discharge 39 from the expansion cooling turbine 2 connects device 14 for separation of condensate phase 32 fro gas phase 40, which connects the next expansion cooling turbine 4 connected to generator 5 for generation of more power 20. From the

phase 33 from gas phase 42, which connects the next expansion cooling turbine 6 connected to generator 7 for further generation of power 20. If it is suitable to use some of the expander turbines for mechanical or hydrautic transferred operation of stationary or mobile machines, this is a possible alternative -the former for example corresponding to turbo compressor 8. From the expansion cooling turbine 6 outgoing flow 43 connects device 16 for separation of condensate phase 34 from gas phase 44, which connects at least one Hquid ring pump 9, or another device with the corresponding function, in order to together with the condensation effect and vacuum pump 10 with or without barometric condensate 34 fall leg with water-seal create redetermiaed negative pressure/vacuum rtthe end^""oTthe-system."Then-gas" piping 44 connects separation device 17 for separation of cooling and sealing Hquid 24 for Hquid ring pump 9 and whereupon the gas flow is pressure increased via at least one fan 11 before gas outlet 45 regarding reaction progress during total oxidation in reaction vessel 1. The high steam partial pressure of the reaction progress counteracts the formation of nitric oxides (KOχ) in the flue gas by a counteraction of uncontroHecL, high temperature level. It is also possible to eliminate already formed nitrogen oxides by injection, 40N, of ammonia ( H₃), and or urea (NHz CO into the flue gas in one or more places, preferably before expander turbine stage. By doing this the nitric oxides will be converted chemically to nitrogen (N₂) and water. The flue gas, by this, gets an increased steam partial pressure, which further increases the physical energy content of the flue gas. At reaction progresses during partial oxidation in the reaction chamber 1, a fuel gas 44 is obtained, which according to the dashed proceeding in the figure, is combusted in gas boiler 12 with possible adding fuel 21, with production of high pressure steam 89, in one with the expander turbine process integrated performance, and operation of steam turbine 120 with generator 121 for further power generation 20 and via separation device 17D recirculation of condensate 88, alternatively with suitable pre-heati g according to 12A and 12B of the condensate flows 32 and/or 33. After gas boiler 12 a gas fan 13 is preferably instaUed The pre-heating can also include gas flows before respective expander stage - the latter cannot be seen in the figure. The procedure thus comprises expansion cooled, clean condensate excess 34 from cistern 19 and is separated for example within the temr^rat e lS-20"^ corresponding to the pressure level 0,03 bar (a) after expansion cooling turbine 6. The low temperature level of the condensate excess 34, without any need of cooling water and by that at a minimum of exergy losses, generates correspondingly more power 20 via generator 7 connected to expansion cooling turbine 6, which is the third and last expansion cooling stage. Expander turbine stages 2, 4 and 6 of the

condensate separation 14, 15 and 16 after respective expander stage or partial stage. If steam production or district heating 23 is required, steam generator or heat exchanger is instaHed on recycling condensate flow 33, or other suitable place, with coτrespondingly lower power generation 20 as a result

Figure 6: The proceeding according to the present figure is essentiauy weH suited for some form of district heating plant suitable for some form of quarter of a town or bigger population centre ^"and le^"Scribes-combustion^"xmder total-oxidation of dry deHvered, or almost dry deHvered, fuel under pressurized reaction progress in reaction chamber 1. The reaction process can be catalysed by addition of hydrogen peroxide solution βiQi) 37, whereupon as well the water steam partial pressure as the physical energy part is increased correspondingly. The gas flows 38, 40 and 42 pass respective cooling expansion stage 2, 4 and 6 with the intermediate devices for separation of respective condensate flows 32, 33 and 34, All the cooling expansion stages and the turbo compressor 8 and generator 3 are connected to a common rotating system. In principal aH the recycling condensate flows 32, 33 and 34 are returned to the reaction chamber 1. Condensation flow 33, when necessary also a part of condensate flow 32, is previously used for district heating 23 with used energy amount adjusted according to needs corresponding to the reduced part of power generation 20. There is a possibility not to utilize the district heating system 23, for example during the summertime, with the accompanying more power generation 20- When excess of power generation 20 this part is fed into the common network. The water refilling or drainage of the system is done by the cooling and sealing water 24 of the liquid ring pump 9 according to the level control 19A at the storage tank 19. When there is water excess in the system the drainage is thus made through the "cold" end The outgoing flue gas 45 is free from all forms of dust particles, volatile metals and volatile organic substances and compounds. The formation of nitric oxides as thermal NO* is counteracted by the high steam partial pressure of the reaction progress. The high total isentropic efficiency makes exceptionally high energy recovery possible by the return of heat condensates and the heat transmission acting direct by the different phases of water as some kind of energy transducer, with a continuing condensation from the very high temperature of the reaction progress down to the outgoing expansion cold flue gas at room temperature.

Figure 7:

comprising a first fuel 30 and a second 30C. possibly w t contcui of water 31 a xά 31C respectively during pressurized reaction progresses in the reaction vessel 1 and 1C during partial and total oxidation respectively by means of additions of compressed air 35 and 35C as oxidizing agents by turbo compressor 8 and additives of recovered chemicals 401 and 401C by one or more processes, 400 and 400C respectively, while the remaining amount of the recovered chemicals is brought out of the proceeding. Depending on type of fuels, with different chemicals content after the reaction progresses a phase of soHd and/or molten material 18 and 18C respectively can be obtained. The outgoing gas phase 38 and 38C ^~ respectively- of thfrϊeaction-chambefs are cooled during condensation-of in- the gas vaporized substances and compounds by expansion cooling. The mentioned gas phases contain fine particular dust which is wetted during the condensation and gets heavier and fans out mainly in the condensate flow 32 and 32 C of respective first stage. Both these condensate flows are returned to respective reaction chamber. Both the oxidation progresses, partial respective total, foHow each other with common expansion cooling down to negative pressure/vacuum, for example 0,03 bar (a) with corresponding temperature level 18-20°C. Each expansion turbine is connected to a generator for power generation 20. The proceeding has extremely low exergy losses, by expansion turbines connected in series with recirculation of energy rich condensate flows with the recovery of as weU the heat content as the pressure energy and with outlet of expansion cooled excess condensate at very low temperature- The recovery of mentioned chemicals 401 and 401C from respective gas phase is thus made by a first process stage 400 in reducing state and by a second process stage 400C in oxidizing state. Within the reducing state the content of the fuel gas of for example hydrogen (H₂) and carbon monoxide (CO) are recovered, according to known procedure, constituting synthesis gas as raw material for the production of for example hydrogen peroxide solution (H2O2) and/or a number of different mobile motor fuels. There are, when fuel 30 containing sulphur, further possibilities for recovering chemicals from the reducing gas according to later described proceedings under chapter The sulphur handling in the form of hydrogen sulphide (H₂S), elementary sulphur (S), hydrogen (H₂) and hydrogen peroxide (H2O2) as a whole or parts of it Within the oxidizing state for example the content of the flue gas of sulphur dioxide (SO₂) is extracted by means of absorption by external and/or by the fuel added alkaH according to later presented proceeding for the production of sulpbite Hquors fNa₂SO₃ /NaHSO₃) for the production of sulphite based pulping quaHties. Some fuels contain slag forming substances and compounds which are separated as a phase of solid and/or molten material 18 which is cooled and/or ti ϊ^ ^ _a ^ superheated or during partial or total moisture satiiration, connects expansion cooling turbine 2 connected to turbo compressor 8. From expansion cooling turbine 2 outgoing flow 39 connects device 14 for separation of condensate phase 32 from gas phase 40 whereupon condensate phase 32 is returned to reaction vessel 1, with partial flows for moistening from reaction vessel 1 outgoing gas 38 and when needed for the treatment of phase of solid and/or molten material 18 at quench 126. Gas phase 40 connects one or more processes 400 for recovering chemicals 401 whereupon the remaining part of the gas phase 402 connects the next expansion cooling turbine stage 4. From the expansion cooling turbine 4 outgoing flow 4 ^{" _}connects-device 15 forse:parationof-eondensate-phase-33--from gas-phase-42, whereupon condensate phase 33 connects condensate phase 32 for common return to reaction chamber 1. The rest of the gas phase 42 is after that totally combusted by a pressurized reaction progress in reaction chamber IC during addition of compressed air 35C and fuel 30C, possibly with water content 31C and part of earlier recovered chemicals 401, whereupon outgoing gas 38C, superheated or during partial or total moisture saturation, connects the expansion cooling turbine 2C From the expansion cooling turbine 2C outgoing flow 39C connects device 14C for separation of condensate phase 32C from gas phase 40C whereupon condensate phase 32C is returned to reaction chamber IC. When there is unbalance between the condensate fractions 32, 33 and 32C, there is a mutual exchange of condensate through flow 33/32C. From the gas phase 40C one or more chemicals 401 C are recovered whereupon the remaining gas flow connects expansion cooling turbine 4C. From this turbine 4C outgoing flow 41 C connects device 15C for separation of the expansion cooled, clean condensate excess 34 from the gas phase 42C, whereupon said gas phase strengthens the negative pressure/vacuum achieved by the condensation effect of the proceeding and by the barometric condensate fall leg with water-seal 34 and vacuum pump 10 and liquid ring pump 9 with the cooling and sealing Hquid 24, which is separated by device 17 whereupon the expansion cooled gas phase 45 is pressure increased by gas fan 11 before the outlet through funnel.

Figure 8:

The proceeding according to this figure describes, like the preceding figure 7, a form of two stage combustion comprising a fuel 30A containing a Hquid possible for vaporization, preferably water 31 A, with the additive of a supporting fuel 30B which fuels are commonly combusted during pressurized reaction progress in the reaction vessel 1 during partial oxidation by addition of compressed air 35 as oxidizing agent through turbo compressor 8. inSl 3θ is r -ie?abiy

recovery of actual agents and/or compounds comprising heavy metals. In order to facilitate an almost complete recovery the two stage combustion with a first stage during partial oxidation is used whereupon foHows a second stage under total oxidation of the fuel gas of the first stage with the turbine expansion cooling of gas flow after respective reaction progress and recycling/separation of respective condensate flow. The proceeding makes fractionated three stage separation possible of actual agents and/or compounds, regarding as weH the oxidation potential as the pressure and temperature: • Separation stage I - 18A - is composed by ash and/or a phase of soHd and/or molten material^" and or heavy metals^" 18 A during 'high temperature-and reducing state. • Separation stage II - 18B — is composed by condensate containing earlier gas carried dust particles and/or volatile agents and/or compounds comprising heavy metals during somewhat lower pressure and temperature compared to separation stage I but still during reducing state. • Separation stage HI - 18C - is composed by condensate mainly containing the rest of eariier volatile agents and or compounds comprising heavy metals during even lower pressure and temperature compared to separation stage II and furthermore during oxidizing state. From reaction chamber 1 outgoing fuel gas 38 of high pressure, superheated or during partial or total moisture saturation, is connected to expansion cooling turbine 2 with connection to air compressor 8 and generator 3 for power generation 20. From the expansion cooling turbine 2 outgoing flow 39 connects the device 14 for separation of condensate phase 32 from gas phase 40 whereupon condensate phase 32 is returned to reaction chamber 1, with a partial flow for moistening of from the reaction chamber 1 outgoing fuel gas 38 and, when needed, for treatment of ash and/or a phase of soHd and/or molten material 18A at quench 126. The fuel gas phase 40 connects reaction chamber IC for complete combustion during total oxidation, whereupon outgoing flue gas 38C, superheated or during partial or moisture saturation, is connected to expansion cooling turbine 2C with adherent generator 3C for power generation 20, From the expansion cooling turbine 2C leaving flow 39C connects device 15 for separation of condensate phase 32C from gas phase 40C whereupon condensate phase 32C is returned to reaction chamber IC with partial flows for moistening from reaction chamber IC outgoing flue gas 3SC and with connection to condensate phase 32. Gas phase 40C connects the expansion cooling turbine 4C with adherent generator 5C for power generation 20. From the expansion cooling turbine 4C outgoing flow 41 C is connected to

42C, whereupon said gas phase 42C strengthens the negative pressure/vacuum achieved by the condensation effect of the proceeding and by barometric condensate fall leg with water- seal and vacuum pump 10 as weH as by liquid ring pump 9, as a whole or parts thereof, with the cooling and sealing Hquid 24/34 which is separated by device 17 whereupon the gas phase 45, in principal consists of carbon dioxide (CO₂) and the inert nitrogen (N₂) origmating from the combustion air, is some pressure increased by gas fan 11 before the outlet through funnel . Back to separation device 14 and outgoing condensate phase 32 with separation of a partial flow 32A, which partial flow is pressure reduced through a Hquid expander 80 with adherent generator-81 for power generation 20 - alternatively a pressure reducing valve — with connection of outgoing flow to device 85 for separation of the condensate phase 18B from the expansion steam 180, which steam flow is connected to eariier mentioned flow 39C before connection to separation device 15. This figure thus describes fractionated recovery, during as well reducing as oxidizing conditions within the same proceeding, through stages 18A, 1 SB and 18C respectively mainly of different types of hazardous waste for example combustion cremation under high pressure/steam partial pressure, whereupon heavy metals as for example quicksilver (Hg), dust particles and the formaldehyde content of the fibreboard coffins are prevented from entering into the atmosphere - while the energy from aU the fuels is essentially recovered as power 20. Selenium (Se) 300 can also be added to one or both the reaction progresses in order to bind the quicksilver, whereupon the selenium, as a part or the whole, is recycled with the condensate flow 32 and 32C respectively.

Figure 9:

This application of the expander turbine proceeding is essentially weU suited within the transport sector. The proceeding is exemplified by expansion cooling in two stages with fuel nearly free from carbon (C) or carbon compounds, whereby the discharge in principle exists of only water/condensate, besides when addition of compressed air the discharge also includes the air content of inert nitrogen Hi). Reaction chamber 1, with pressurized reaction progress during total oxidation, is fed with fuel and oxidizing agents comprising part of parts of: hydrogen peroxide (H₂Q₂) 37, constitutes an integrated form of fuel and oxidizing agent, or as hydrogen peroxide solution (E-₂O2 * nlhO 37, hydrogen (H₂) 68, oxygen (O₂) 36, turbo compressed air 35, ozone (O₃) 115 according to one or more of the equilibrium/decomposition reactions below: H₂O₂ >ri₂G ÷ l/20₂

H₂O * nE₂0 - B.2 O (2+n)E₂0 3/2O₂4- 4H₂ + H2O2 * nH 0 <=> (5+n) ₂0 comprising added compressed air/oxygen. O₃ <=> O₂ + O, representing one of the possIbfHtϊes to add oxygen (and physical energy) Hydrogen peroxide 37 has a huge thermodynamic energy content, which means that huge amounts of energy are released when peroxide decomposition during the reaction progress. Furthermore hydroxide radicals are formed, which give an efficient and even combustion at comparatively low temperature. There is also a possibility to render more effective and to pressurize the reaction progress by adding some form of activator 30 in order to increase the decomposition reaction rate of fee-hydrogen peroxide,- even-though the hydrogen peroxide naturally has a great instabiHty. The burner system in reaction chamber 1 consists preferably of at least one venture-nozzle for actual additive flows. During the reaction progress produced steam flow (5+n)H2U 38, superheated or during partial or total moisture saturation, is cooled during steam condensation by expansion cooling through expander turbines 2 and 4, simultaneously as the steam flow content of physical energy is transfoπned to mechanical work via expander turbine connected turbo compressor 8 and generator 3 with possibility to reversing at start up and generating of within the process needed power 20, among others for charging the storage battery/accumulator 3 A and for operation of pumps, fan etc. and power transmission including hydrauHcs with shaft-coupling 83B and gear 83 C for operation of mobile engine/vehicle 83 A. Alternatively (can not be seen infrgure) a fuel cell process for the production of electricity 20 is integrated and with pressurized fuel cell also integration/connection of steam to expander. The outgoing steam/condensate flow 3 of the expansion turbine 2 is connected to device 14 for separation of condensate flow 32 from the remaining steam flow 40. The recycling condensate 32, comprising of among others the water content ( U₂θ) of the hydrogen peroxide solution 37 and the by equilibrium formed steam (5+n}H₂θ, control the intensity of the reaction progress and thereby the water thus constitutes some kind of modulator with among others limited NOx-for ation. The exothermic reaction heat of the reaction progress and the endotherotic vaporizing work is by that balanced with regard to the ultimate energy recovery in connection with the turbine expansion cooling. Both the water additives as weH as by the equiHbriurn formed amount of steam during the reaction progress thus increase the total amount of steam and by that also the physical energy level of the system. Eariier mentioned, possible addition of activator/catalyst 30 is recycled to a certain extent with condensate flow 32. Back to the remaining steam flow 40 which is connected to the next expansion turbine 4 constitutes the last expansion cooling stage. The

ma taining necessary negative pressure/vacuum at the end of the system, besides through the condensation effect by means of fluid ring pump 9 with internally cooled condensate 34 forming cooling and sealing Hquid 24/34, which is separated/recycled via separation device 17, further connecting for increased condensation effect a number of heat exchangers/vaporizers 36B, 37B. 68B and 115B for according to mentioned above, alternative fuel/oxidation additions as oxygen 36, hydrogen peroxide 37, hydrogen 68 and ozone 115 from respective tanks 36A, 37A,68A and 115A. These tanks are preferably pressurized, with preferred content of Hquefied gas and isolated Hydrogen H₂ 68 is kept cool in the tank 68 A - whereupon the subsequent vaporizer 68B, also comprising -a cooler for liquid hydrogen in the tank 68A- The cooling capacity of the heat exchangers vaporizers at flow 41 with the ending liquid ring pump 9, thus creates a predetemi ned negative pressure/vacuum - for example at the discharge pressure/counter-pressure 0₃05 bar (a) of the expander turbine 4 the corresponding temperature is around 23°C, comprising the rest condensate. After the separation device 17, when needed, fan 11 is installed in piping 45 for discharge of start up steam. There is a possibiHty, into the air/oxygen flow O₂ direct initiate a certain amount of ozone 0₃ by the supply of electrical energy or ultraviolet radiation 115C, or other known proceedings, when the system 115A/115B for supplying ozone can be a complementary or excluded. Preferably the reaction progress into the reaction chamber 1 is pressurized by the exothermic reaction progress of the additives, comprising its decomposition reactions, and by the endomerrnic evaporation of the water/condensate as an effective process modulator.

27*g sulphur handling A real technological breakthrough is according to the present invention the possibiHty of the proceeding to separate from a feel almost aH of the sulphur content in reduced form as hydrogen sulphide (H₂S) as a raw material for diversified further production of hydrogen (H₂), hydrogen peroxide (H_{2 2}) and elementary sulphur (S). The recovery of hydrogen sulphide from a gas can be made by allowing the gas to pass a gas wanin apparatus for selective and regenerative absorption of the H₂S-content according to known procedure. Examples of such absorption processes are the Purisol process which utilizes N- methylpyrroHdone as an absorption Hquid, and the Dow Gas/Spec-process which utilizes methyldiethylanxϊne (MDEA) as the absorption agent The utilization of hydrogen sulphide as a raw material can be made by reversible thermal decomposition during heating above temperature 300°C, preferably by one with the recovered liquid sulphur counter-currently

XS -r S^2' =?> Sx ' or recovery of sulphur in elementary form according to H₂S ^ H₂ + S The recovery and decomposition of hydrogen sulphide direct from a gas containing hydrogen sulphide is possible through a, preferably pressurized, antbraquinone (AQ)/anh^ydroquinone (AHQ)-proceeding according to principle diagram, figure 10- Hydrogen H₂ can be used, besides present invention, also within the pefroleum refining industry, to fuel ceUs — preferably pressurized - or for further production according to below. There are also posribiHties for further production of for example ammonia (NH₃) and άnnefhyl ether (DME) ^{" "}andmStfranϋl {CΕLsOW)-oτ other mobile fuels. At recovering these products -from bio fuels - for example waste/spent Hquors when chemical pulp production - so called "green" mobHe fuels is obtained with the expansion cooling proceeding as a preceding gas cleaning and power generation stage. Elementary sulphur or polysulfϊde can be used according to later exemplifications. The company Marathon OH Co, US has developed the so catied Hysulf-process for the conversion of H₂S to H₂ and S as partial replacement for the so catied Claus process. The company also describes the possibiHty to produce as an alternative to H₂ instead produce 0₂ via an H₂Q₂ -intermediate stage. Marathon OH Co's patent document US 4, 581,128 describes in no way the possibiHty/prαpose to produce hydrogen peroxide. The Hysulf-process is similar to customary processes for the production of hydrogen peroxide by the utilization of reaction of anmraquinone (AQ) to anfhrahydr oquinone (AHQ), followed by the regeneration stage AHQ to AQ. The hydrogen gas formation according to the Hysulf-process is made by catalytic dehydro generation. Conventionally almost ah H₂O₂ in the world is produced by the anthraquinone method - the AQ- ethod. The reaction is done by stepwise hydro generation and oxidation of alkyl anth quinones when hydrogen peroxide is formed The possibility to use anthraquinone according to present invention also means absorbing of hydrogen sulphide direct from for example fuel gas for the production of elementary sulphur, hydrogen and/or hydrogen peroxide according to principal diagram, figure 10, with integration of the sulphate pulp process according to block diagram, figure 11. This figure describes the possibility to coordinate a preferably pressurized AQ handling with the sulphate pulp cooking and the chemical recovery by a part of nearly sulphide free white liquor or low sulphidity white liquor receiving "used" AQ with new charge/refill to the recovery for necessary renewal. Recovered elementary sulphur is added to the remaining part of low sulphidity white Hquor for the production of pulp yield increasing poly sulphide solution (Sχ^2") according to:

Detailed description is foHowing in figures 10 and 11. Figure 10: Pressurized gas 40 A containing H₂S is fed to a reaction chamber 61 where the anthraquinone (AQ) is transformed to anfhrahydr oquinone (AHQ). A subsequent separation stage 62 separates elementary sulphur (S) 69. A regeneration stage 63 reforms the anthraquinone (AQ). After the separation stage 64 the anthraquinone solution 65 is recycled to the reaction stage 61 for further one, preferably pressurized sequence, and so on. Touring the second separation - stage 64- re deHvered, besides the gas40B freed-from hydrogen sulphide (H₂S), also hydrogen (H₂) 68 and / or (H2O2) 37. The hydrogen 68 formation requires a catalytic dehydro generation - which is not shown in the figure. Hydrogen peroxide (H₂O₂) 37 is formed through oxidation by oxygen containing agent - for example air 35 and/or oxygen (O₂) 36.

Figure 11: This figure comprises appHcation of method according to figure 10 within the sulphate process of the pulp industry with process integration of the pulp production and the chemical recovery. Waste Hquor/release liquor from sulphate pulp digester 50 passes DS-increasing process stage - preferably evaporation plant— however not shown in figure - whereupon DS- a ount 30 with remaining water content 31, also named black Hquor, connects one or more reaction chambers 1 together with compressed air 35 for reaction progress during partial oxidation. From the reaction chamber outgoing fuel gas 38 passes a first expansion cooling turbine stage 59 with power 20 generation, whereupon outgoing fuel gas connects the process stage, according to figure 10, for decomposition of the H2S part. Recycled condensate 32 from the expansion stage connects reaction chamber 1 as a whole or as a partial flow. Fuel gas 40B, treated regarding H₂S, passes a second expansion coohng turbine stage 60 for further power 20 generation. Separated condensate 33 containing dissolved carbon dioxide (somewhat lower pH) is used for improved pulp 53 washing- As the principal part of the sulphur content of the black liquor is driven out with the fuel gas as H₂S, the melt phase 18 from the reaction progress contains mainly sodium carbonate (Na2CO₃) and sodium hydroxide (NaOFT) with a strongly restricted amount of sodium sulphide (Na₂S). This means that from reaction chamber 1 leaving green Hquor 18 constitutes nearly sulphide free green Hquor. Non process elements (NPE) are ehrninated by a sludge filter and nearly sulphide free green Hquor is causticised 51 whereupon part of nearly sulphide free white Hquor 55 is mixed with elementary sulphur 69

sulphate pulping process. An advantage at causticising 51 of nearly sulphide free green Hquor 1 , for production of nearly sulphide free white Hquor 55, is the low part of sulphide (NaHS) whereby the caustification degree wfU be higher by changing the ion strength relation positively. The remaining part of nearly sulphide free white Hquor 55 is mixed with the exchange part of recycled antraquinone solution (AQ) 65 into rnixer 70 whereupon the cooking solution 56 connects the final part of the pulp cooking. Refill is evident from the flow of antraquinone solution (AQ) 67- Further a possibiHty to direct produce cooking Hquor 56 is to add, as a part of or as a whole, exchanged recycled AQ solution 65 into mixer 70 and ^■ neariy-sulp de -free-green Hquor-18A - broken Hne--in figure.- Produced -hydrogen peroxide (H₂0₂) 37 is used for pulp bleaching and/or as an oxidizing agent/fuel in the reaction chamber 1. The arrangement after the expander turbine stage 60 comprises negative pressure/vacuum generation equipment as well as combustion of fuel gas 40B and cannot be seen in figure 11 but is valid according to the foHowing figure 12.

Figure 12: The figure further describes a proceeding regarding the utilization of the present invention - among others an almost total separation of alkaH and sulphur - and the possibiHty for only causticising of a small partial flow of nearly sulphide free green Hquor. Parts of the positioning used can be found in the eariier text for figure 11. When gasification, partial oxidation, of waste Hquors from the pulping industry two different kinds of reaction progresses with separate reaction chambers, 1A and IB respectively, are used composed of at least one chamber of each during quite different process criteria, A first reaction vessel 1 A works according to the most preferable carrying out of this invention for among others separation / spHt of alkaH and sulphur while the second reaction stage IB works during quite different, "opposite", criteria as low process pressure, preferably 1,10 - 4,00 bar (a), with low steam partial pressure, preferably 0,20 - 0,95 bar (a) and within the temperature interval 920 - 1000°C with supplying recovered elementary sulphur (S) 69 for direct conversion production of high sulphidity white Hquor (ISfajS) by displaced reaction equihbrium during the reaction progress in the second reaction chamber IB according to: Na₂CO₃ + H₂S <=> Na₂S + H₂O + CO₂ SuppHed ϊntemaHy recovered, elementary sulphur S 69 is during reaction progress reduced to hydrogen sulphide (H-S) with subsequent equiHbrium displacement according to above towards right By that means high sulphidity white Hquor Is direct produced without any need

proceeding according to the present figure. Earlier described proceedings to use K₂S as a raw material for further production according to figures 10 and 11 are included in applicable parts in this figure 12. Reaction chamber I A thus works during operation criteria for the separation/spHt of alkaH and sulphur with the later as H₂S in the fuel gas 38A. Reaction chamber IB thus during quite different operation criteria, according to above, and the quite decisive supplying of internal within the process recovered elementary sulphur (S) 69. In this way the dommating part of sulphur is displayed to the melt phase of the second reaction stage in the form of sodium sulphide (N S) 18B. The remaining sulphur is to be found in gas phase -38-B ^•asΗ₂S therefore the gas phase is eompressed -in tαrbo compressor 82, with in-tapping to expansion turbine 2 which is also fed with fuel gas 38A from reaction chamber 1 . From the expansion turbine 2 outgoing flow 39 contains by that as weU gas phase 38A as 3 SB and is connected to separation device 14. Here the gas/Hquid phase 39 is separated with gas phase 40 fed to the next expansion cooling turbine 4 whereupon the outgoing flow 41 is connected to separation device 15. Here the gas phase 42 and condensate phase 33 with partial flow 33 A is separated which together with condensate phase 32, with the content of among others earlier vaporized hydrocarbon compounds and gas carried dust particles, from the preceding separation device 14 is added to reaction chamber 1 A with adherent melt dissolver 126A as one or more partial flows — among others flow 321 to the preparing evaporation plant and for moistening from reaction chamber outgoing fuel gas 38 A. Reaction chamber 1A is feed black Hquor with the DS-content 30 and water content 31 and when appropriate also bleach plant effluent 87. There is also a possibility to add hydrogen peroxide (B._{2 2}) to reaction chamber 1 and IB as a both fuel and oxidizing agent The normal case for oxidizing agent corresponds to oxygen 36 to reaction chamber 1 A and by high pressure fan 84 for air 35B to reaction chamberlB. Back to separation device 15 with the subsequent gas phase 42 and condensate phase 33 with partial flow 33 A according to above and a partial flow 33B to reaction chamber IB with adherent melt dissolver 126B. The condensate recovery is segregated and the conditions for process integration are controlling the water balance. When excess of condensate phase 33 the condensate 86 is used for example for pulp washing. Back to gas phase 42 with content of H2S, among others from the collected "heavy⁵' gas system, non condensable gas (NCG) 90 of the rniH, which is connected to device 61-64 for the decomposition spHt of H₂$ according to eariier described proceedings. Back to reaction chamber 1 A with outgoing, pressurized green liquor flow 18A of almost sulphide free alkali or low sulphide alkali, which is depressurized, for example by a Hquid expander 80 with or

ISA and expansion steam are separated through separation device 85. Green liquor ISA is treated with pressure filter 95 for the separation of non process elements (NPE) 54 before the caustffication plant 51 for production of nearly sulphide free white liquor or low suffidity white Hquor 55- When need of nearly sulphide free green Hquor 18A, according to figure 11 , a partial flow is drawn off before causticising 51 with direct production of cooking liquor 56 by adding in mixer 70 the exchange amount of recycled AQ-solution 65 together with nearly sulphide free green Hquor 18 A - aH according to figure 11. From the device 1-64 for decomposition of H₂S, partial flows of H₂ 68, H₂O₂ 37, and S 69 and when appropriate the -flowAiQ 65 is"leaving. The hydrogen fraction 68 can at-fhe expense of the peroxide production (H2O2) 37 be further refined in another way according to earlier description. After the removal of the H2S-content of the fuel gas the gas flow is expansion cooled by a third expansion turbine stage 6. AH three expander stages are provided with generators 3, 5 and 7 for power 20 generation, alternatively with expanders' power transmission for operation of engine / machine. The first expander stage 2 is furthermore provided with start up function for the turbo compressor 82 in the form of an electric motor 83. The gas flow 43 after the third and last turbine stage 6 connects separation device 16 with separation of gas phase 44 and Hquid phase 34. The counter-pressure for the expander turbine 6 is quite decisive for the outlet temperature of gas respective Hquid phase/excess condensate 34. When for example the outlet pressure 0,05 bar (a) the corresponding outlet temperature around 23°C is obtained. The very low temperature/pressure level of the leaving flow from the last expansion cooHng stage 6 lowers in the corresponding way the exergi losses and increases the generation of power 20. The negative pressure/vacuum of the system after the last expansion cooling stage is supported, besides the condensation effect itself, by some suitable process technology as Hquid ring pump 9, fan 11 and by barometric condensate 34 fall leg with water-seal and vacuum pump 10 as a whole or parts thereof, and storage tank 19 for cooled, clean re-useable condensate excess 34. The gas phase system 44 is co-ordinated with from the evaporation plant originating NCG-system 90. When needed, a system of Hquid ring pumps connected in series, is used and when the cooling and seating Hquid 24 suitably is led in counter-current to the gas direction for stepwise gas washing. The cooHng and sealing Hquid can also be made of an alkaline Hquid 24A, 55 for selective absorption of the rest-H₂S. One form of performance is when a last liquid ring pu p is used as a final wash stage with cold, clean water as a cooling and sealing Hquid 24, 34 according to figure 25. Another form of performance is a Hquid ring pump of type multi wheel, where the number preferably is limited to one single

fluid 24 are separated by separation device 17 whereupon the gas phase is pressure increased by fan 11 with gas connection to gas boiler 12. There is a possibiHty to utilize additional fuel 21. Gas boiler 12, with air addition, is utilized in a conventional way by steam production 89 via boiler feed water 88 or preferably by reheating of internal flows before and/or between the expander stages - for example flow 39. Everything that feeds physical energy to the system has priority. After the gas boiler 12 foUows flue gas condensation 22 and fan 13 with flue gas 45 outlet in principle as SO₂-free carbon dioxide CO₂, which as an alternative can be recovered. Back to reaction chamber IB the process of which during the reaction progress is ^•justabove atmospheric pressure, which makes it possible to by fan- 84 feed air 35B as an oxidizing agent When need for poly sulphide 58 elementary sulphur 69 is added to low sulphidity white Hquor 55 for poly sulphide production: S + S^2~ < Sχ^z~ Accordingto description, figures 11 and 12, there is thus a possibiHty of direct production of high sulphidity white Hquor 1 SB, without previous causticising, meant for the pre frearment intxoductory part of the pulp cooking. From the description can also be seen direct production of cooking Hquor 56 without preceding causticising, meant for the finish part of the pulp cooking, by mixing AQ-solution 65 and or 67 with nearly sulphide free green Hquor ISA into a mixer 70. The need of the conventional causticising does not occur as the separation need of necessary amount of carbon dioxide (CO₂) is done already during the equilibrium displacement of the reaction progress in reaction chamber IB, to the right according to the equHibrium reaction below, with direct production of high sulphidity white liquor 18B: Na₂CO₃ + H₂S => Na₂S + H₂O + CO₂ By that remains only a need for causticising of a small part of nearly sulphide free green liquor flow 18A in the main intended for the bleach plant The proceeding further comprises a ^" possibility to strengthen the sulphur content in reaction chamber IB as black Hquor feed 30, 31 — before reaction chamber IB — selectively absorbs part of the combustion gas 38B content of hydrogen sulphide H₂S -which cannot be seen in figure 12.

Figure 13: The figure comprises recovery of energy and chemicals from a fuel which consists of sulphur rich hydrocarbon compounds during pressurized reaction progress in reaction chamber by understoichiometric combustion during high steam partial pressure. The figure describes two

and the other comprises fuel with content of alkaH compounds - or when alkaH compounds is added in another way. The later procedure, comprising alkaH compounds, has in the figure the corresponding flow Hues broken, h general, chemicals are recovered from hydrogen sulphide H₂S by eariier under figure 10 described AQ-/AHQ-ρrocedure or another procedure with corresponding function, comprising the recovery of a part or parts of: hydrogen peroxide H₂O₂37, hydrogen H₂ 68 and elementary sulphur S 69, with the possibiHty to be recycled within the proceeding and/or to be brought out for other purposes. By the distinctive of the proceeding the outgoing flue gas contains nearly only carbon dioxide CO₂ which make it possible to^~be ecoveredforτecircnlation 45A and also to be liquefied -and brought out 45B for other markets or final waste disposal, for example, deep into fuel weUs as a working fluid for the fuel- The positions correspond to eariier descriptions among others according to figures 1 , 11 and 12 with complementary additions according to this figure for the in- and outgoing fuel gas 42 A and 42B respectively of the AQ-/AHQ-proceeding 61-64. Gas boiler 12 produces high pressure steam 89 feeding the steam turbine 120 with counter-pressure steam 89A. Steam turbine equipped with adherent generator 120 for power generation 20. The reaction progress oxidizing agent constitutes of oxygen O₂ 36 and with addition of within the procedure produced hydrogen peroxide H₂O₂ 37. It is also possible to add to the reaction progress internaUy produced hydrogen H₂ and elementary sulphur S 69, which is a carrier of hydrogen H. When the proceeding is covering alkaH, broken lines in the figure, either added by the fuel 30 or as an addition 55, a catalytic effect on the combustion process is obtained, the alkaH melt is separated dissolved after the reaction progress in quench 126 as an alkaH solution 18A, which is cooled through heat exchanger 118 and thereafter through cooler 119 with necessary pressure decrease before connection to Hquid ring pump 9 as combined cooling and sealing water 24 alkaH solution ISA for mainly absorption of in the fuel gas remaining hydrogen sulphide H₂S, whereupon the outgoing cooling and sealing water 24/alkaH solution 18B, now with sulphur content via heat exchanger 118 connects reaction chamber 1, whereupon the sulphur is desorbed as H₂S and thereafter is to be found in the flue gas flow 38. Present proceeding prevents the release to atmosphere of dust particles, volatile organic agents and compounds as weH sulphur compounds as carbon dioxide and also minimizes the formation of nitric oxides NOχ. Besides the mentioned, diversified chemical production also recovery of a number of "green" energy forms from fossil fuels/waste is possible, for example petroleum coke 103. in the form of power 20 via turbine connected generators 3, 5, 7 and 121 and as steam 89A as weH as a number of mobile fuels. Figure 14: The present figure constitutes a modification of the previous figure 13 comprising integration of a pressurized fuel ceH procedure, for power generation, with for the reaction progress in the reaction chamber and fuel ceH co-ordinated addition of oxygen and with addition of hydrogen H₂ to the fuel ceH from eariier, under figure 10 described AQ-/AHQ-procedure, or another procedure with the corresponding function. Energy is thus recovered by partial combustion of ^"a

alkaH. When lack,- or insufficient amount of sulphur and/or alkaH this is added to the reaction progress for a partially cycHc process comprising selective absorption and decomposition of the fuel gas content of hydrogen sulphide H₂S by the mentioned AQ-/AHQ-ρrocedure for production of elementary sulphur S, hydrogen H₂ and/or H₂O₂ whereupon the process comprises absorption of the fuel gas content of HzS-rest and a part of the carbon dioxide CO₂-content by the from melt dissolver of the reaction chamber recycled alkaH solution with completion of fee cyctic process by desorption of the mentioned H₂S and CQ2 during the reaction progress in the reaction chamber according to the equilibrium reactions below. Absorption: Na₂COs + H₂S => NaHCO₃ + NaHS Na₂CO₃ + CO₂ + H₂O = 2 NaHCO₃ Desorption: NaHCO₃ + NaHS => Na₂CO₃ + H₂S 2 NaHCQ3

+ CO₂ + H₂O The recirculation thus comprises elementary sulphur S as a carrier of hydrogen H in the form of hydrogen sulphide H₂S and by the alkali solution as a carrier of the fuel gas content of rest- H₂S and the amount of carbon dioxide. Besides the high process pressure in the reaction chamber 1 the split of sulphur and alkaH is favoured by the high partial pressures of steam as well as carbon dioxide during the reaction progress according to the below equilibrium reaction with displaced equilibrium towards the left Na₂CO₃ + H₂S = Na₂S + H₂0 + C0₂ The proceeding according to figure J 4 comprises mainly eariier made positioning, why the figure description obtains a more comprehensive positioning. When fuel 30 lias lack of sulphur S 69 and/or alkali 55 these chemicals, according to a refiH procedure, is thus added to flow.

chemicals wiH be in excess, and is recovered from the procedure as elementary sulphur S 69B and alkaline solution 18 C The chemical recovery comprises according to above also hydrogen 68 for pressurized fuel ceH 122 and hydrogen peroxide H₂O₂ 37, with possible addition 37A to the reaction chamber 1 while possible excess 37B is brought out from the procedure. The fuel gas content of chemical energy is combusted in gas boiler 12 for production of high pressure steam 89 and the operation of steam turbine 120 with adherent generator 121 for power generation 20. The total energy recovery of the proceeding thus comprises power generation 20 by pressurized fuel ceH 122 and by generators 3, 5 and 7 ^"crnhected to eiφanderTurBhies andsteam turbines 120 and I24^after steam^~production in gas boiler 12 and after pressurized fuel ceH 122 with connected generators 121 and 125 respectively, and when needed tapping off necessary amount of steam 89A and 89B. Flue gas 45, after gas boiler 12 with subsequent flue gas condensation 22, constitutes in principle of only carbon dioxide CQi, suitable for a liquefied recovery for other markets or long time storing into wells/aquifers as a working fluid for feeding the fuel 30. The expansion of the integrated procedure to negative pressure vacuum, for example 0,05 bar (a), minimizes the exergy losses with the corresponding maximization of fee power generation 20, which means outlet of clean, cold condensate excess within the temperature area of 21 - 25°C

Figure IS: An interesting integration possibility between the present invention and the pulping process is the proceeding with combustion under partial oxidation according to figure. The integration is in principle vaHd both for the sulphate as partly also the sulphite pulping processes and comprises the fibre process chip bin 97, chip pre-treatinent 98 and pulp washing 99 together with production of nearly sulphide free white liquor 55 and high sulphidity white liquor 55A. The eariier figure descriptions with corresponding positioning are vaHd in appHcable parts, why figure 15 obtains limited description with appHcation for sulphate pulp production. One of the procedure forms of the reaction process is made by understoichiometric combustion of sulphate soap 102 as a first step during the reaction progress with ring-shaped, pneumatic dry added sulphate ashes 101 and/or petroleum coke 103 forming a second stage in the reaction progress with pneumatic means of transport preferably consisting of oxygen containing gas and or steam. After the first expansion stage with condensation out of the fuel gas content of vaporized agents and/or compounds and dust particles (diameter from 0,01a) the pressurized hot and humid fuel gas 40 with H₂S-content thus with the dust particles removed, is used for

with return of preheated fuel gas 40B to the next expander cooling stage 4. Separated condensate 32 and/or 33A, or other flows, are also preheated to maintain the highest possible total physical energy level for optimal power 20 generation. There is a possibility for a conventional flue gas condensation 22 after the gas boHer 12. When during the eariier condensation out of the fine dust particular content of the fuel gas after the reaction progress, the particles are used as condensation nuclei during the condensation process, whereby the particles are wetted/get heavier and transferred from gas phase to the Hquid/condensate phase. The cooHng and sealing Hquid 24 of the Hquid ring pump 9 consists of cooled nearly sulphide - freer white- Hquor 55 or nearly sτnpMderiree- green-liquor 1-8, the latter-alternative cannot be seen in figure, for against CO₂ selective ^S-absorprion by the dynamic shaping of the proceeding with extremely short absorption time of contact, forming the second H₂S- absorption stage. The third and last absorption stage for the remaining H₂S consists of chip bin 97 with operation around atmospheric pressure -just above or below. This stage 97 consists of chip preheating with moisture equalization of the moisture variations of the incoming chips 96. The integration with present Hquor evaporation comprises among others the connection of not condensable gases NCG 90 to a common negative pressure/vacuum system 44. FinaHy, segregated condensate excess 33, with the content of dissolved carbon dioxide, is utilized for pulp washing 99. The outlet/counter pressure of the gas/condensate mixture 41 of the last expansion cooling stage 4 settles the temperature of the outgoing condensate 33. At for example outlet pressure 0,70 bar (a) a temperature around 63 °C is obtained. The described system based on two expansion cooling stages can of course be used for further expansion cooling stages.

Tlie integration of the sulphate pulyτns proces Figure 16:

The principle for the integration of the pulping process can be seen in this block diagram by the three partial blocks DELΪGNIFICATION PLANTS PULP WASH 50/87A/99 and EVAPORATION PLANT 93 and GASIFICATION PLANT, RECOVERY OF CHEMICALS AND ENERGY 150. The deHg fication comprises as weH cooking 50 as bleaching 87A. Wood chips 96 connect block 50/87A/99, the waste liquor of which containing dry substance (DS) 30 with water content 31 connects block 93. From Mock 50/87A/99 the final product bleached sulphate pulp 53 is produced. Oxygen 36 is fed to this block, forming co-ordinated deHvery to block 150 - as an alternative / complement to compressed air 35 as oxidizing

between block 93 and block 150. Block 93 deliv rs black Hquor 30/31 and dirty condensate 120 containing almost ah of the condensable part within block 93 in around 3-4 volume % of the total condensate flow of the block as among others sulphur compounds >98%, turpentine, methanol and ammonium- This condensate flow 120 can with advantage be preheated within the gas bofier 12 before connection to reaction chamber 1, all within block 150, Further from block 93 non condensable gases (NCG) 90 is fed to one with the block 150 common system for negative pressure/vacuum- Block 150 receives clean condensate 151 from block 93 and brings back the condensate flow 32 of the first expansion cooHng stage - the whole or parts of it containing-condensed agents -and/or compounds — as flow 321-.- Further -from -block 150 is deHvered steam 89 from the gas boiler and outgoing flue gas 45. Block 150 also generates power 20 and recovered chemicals, Na- and S- compounds separated, in fee form of NaOH 55 and NaHS 55A respectively to block 50/87A/99, and condensate 33, clean and tempered suitable for re-utilization/pulp washing. Block 150 further delivers one condensate excess 34, clean and cooled, also suitable for re-utilization or out to recipient. Within the block 150 occurring metals/non process elements (NPE) 54 and chlorides are separated from the mill Hquor cycle.

Figure 17:

The principle for the integration of a sulphate pulping process can be seen more in detafi in this figure, forming one of more possible integrations. The present figure describes an turbine expansion cooled procedure based on segregated condensate recovery by means of four expansion cooling stages with advanced, closed and pressurized chemical recovery comprising the release Hquor/black liquor of the digester to the re-charged white Hquor to fee digester in the form of nearly sulphide free white Hquor or low sulphidity white liquor and high sulphidity white Hquor. As this figure has been positioned corresponding to earlier figures fee proceeding is described in a simplified way mainly comprising newly initiated process stages and apparatus as chips pre-treatment 98, digester 50, "Hmited" alternatively conventional evaporation 93, DS-increasing process technology as for example membrane separation (87A) for bleach plant effluent 87, pulp washing 99, connected stearn/"strong" gas systems including non condensable gases (NCG) 90, separation of metals/non process elements (NPE) 54, weak Hquor 94 of the caustification plant is fed to the melt dissolver 1 6, process stage for selective absorption of hydrogen sulphide (H₂S) from the fuel gas by means of counter-currently fed nearly sulphide free white Hquor 55 or nearly sulphide free green

best selectivity of H₂S against C0₂, during extremely short contact time between the gas and the Hquor for the production of high sulphidity white Hquor 55A or high sulphidity green Hquor. The fourth expander stage 6A with adherent generator 7A for power generation 20, like the previous expander stage, alternatively with mechanical or hydraulic power transmission for engine/machine operation. The cooHng and sealing liquid 24 for Hquid ring pump 9 consists of cooled condensate excess 34, also used as an extra process stage for gas wash. Segregated condensate flows 32, 33, 33 A and 34A respectively have been marked in the figure with thick lines. The entire chemical recovery as from the outgoing release Hquor ^~5Θ; 3"fof the-digester up-to-nearly-s lplτide-free white Hquor-55 and high sulphidity white Hquor 55A to the digester 50 comprising a closed high pressure system with pressure level adapted to the process pressure of the digester. Separate process stages within the Hquor evaporation 93 are however preferably at lower process pressures. The process pressure of the reaction chamber 1 is preferably higher than the mentioned high pressure system.

The sulphite pulping process_* with base όfNu Within pulping industries with production of as weU sulphate as sulphite based pulp qualities, the latter comprising bisulphite, NSSC, "cross recovery", CT P etc. and can by present invention use existing, both sulphate and sulphite waste tiquors, during common reaction progress for direct conversion to active cooking chemicals in the form of sodium sulphite aSOs) solution and or sodium bisulphite (NaHSOs) solution. The fuel of the reaction progress consists besides of cookmg/bleaching waste Hquors also of sulphate soap, sulphate ashes (Na₂SO₄) and petroleum coke with S-content (3-4%) being both S-refill and fuel addition. The combustion takes place during partial oxidation with reaction progress during high process pressure, high steam partial pressure and the lowest possible operation temperature from carbon conversion point of view. By that nearly aU sulphur is driven out with the fuel gas in the form of hydrogen sulphide (H₂S). The relation of the carbonate solution between produced sodium carbonate (Na₂CO₃) and sodium bicarbonate (NaHCO₃) is settled in the melt dissolver/quench direct after the reaction process by means of controUed absorption of the carbon dioxide (CO₂) content of fee fuel gas according to: Na₂CO₃ + H₂O + COa *> 2NaHCO₃ as one single carbonate solution or carbonate and bicarbonate solutions as separate flows. There is also a possibiHty for separate reaction chambers with respective melt dissolver/quench for separate production of the carbonate solutions. Silicon (SI) from silicon

content of H₂S Is combusted in a later process phase whereby the H₂S is oxidized to sulphur dioxide (SO₂) and the carbonate solution/s/ absorb/s selectively the SO₂ content of the flue gas for conversion to active sulphite cooking liquid as one solution of Na₂SO₃ and/or NaHSO₃ or as separate solutions according to below. This can be preceded by a process stage for absorption of SO₂ in water. The proceeding means among others the possibility to two stage alkaH sulphite cooking process with sulphite/bisulphite solution preferably in the first stage — the impregnation stage:

- ^■ -NaHCOs + Sθ₂ <=>-NaHSO₃ +-CO₂ - ^■ 2 Na₂CO₃ + H₂O + S0₂ o Na₂SO₃ + 2NaHCO₃ NaHCO₃ + H₂O + S0₂ => a₂SO3 + 2H₂O + 2CO₂ The above is, as can be seen from the equiHbrium reactions, a direct conversion process with separation of alkaH metals and sulphur compounds. The SOz-absorption is pH-adjusted suitably by alkaH, NaOH, for optimal absorption. The carbonate solution which is free from bicarbonate NaHCO₃ contains in most cases besides carbonate Na₂CO₃ also a small amount of NaOH which at the SO₂ scrubber stage reacts according to below: 2 NaOH + S0₂ <^ Na₂SOs +^■ H₂O Only a small amount of the carbonate solution which is meant for production of sulphide free or nearly sulphide free alkaH, for example the bleaching process and pH adjustment needs thus to be.causticised. Gas carried dust particles originating from the reaction progress constitutes condensation nuclei during the condensation, whereby the weight of the wet dust particles are increased whereupon these dust particles are transformed from fee gas phase to the Hquid/condensate phase, together with eariier vaporized agents and compounds after essential condensation during the first expansion cooling stage, whereupon this condensate flow is fed to a preparing stage for the fuel - for example black Hquor evaporation or cortesponchngly — and/or returned to the reaction chamber together with the added black liquor and fed to the subsequent stage 126 for dissolving/cooHng the phase of soHd and/or molten material with partial or total moisture saturation of the outgoing fuel gas 38 before and/or after the sofid phase separation. The outlet/counter pressure of the last expander cooHng stage constitutes preferably a negative pressure/vacuum for predestined cooling effect wife. low temperature of the condensate excess. By that the exergi losses of the proceeding are mimrnized during the corresponding optimization of the power 20 generation or other forms of the energy recovery. According to the present invention the chemical cycle of the πrfll is

extremely difficult to catch, and according to above transferred to fee liquid phase, with final return to the cooking Hquor preparation, which at fee same time also obtains the sulphur in return by absorption of the S 0₂ content of the flue gas in a later process stage. The above sulphite recovery process is exemplified through next figure 18.

Figiwe 18: The fuel to the reaction chamber 1 is fed in the form of either sulphate waste liquor and/or sulphite waste liquor 30 with water content 31 with the addition of bleach plant effluent 87. sulphate ash T01, sulphate^~soap 102, sϋlphύf 69 andpefroleunrcbke 103 ~as a whole oτ part of, with combustion during partial oxidation by means of compressed air 35 and/or oxygen 36-, and hydrogen peroxide (H₂O₂) 37 as an option. The outgoing pressurized fuel gas 38, of preferably high steam partial pressure contains volatile organic agents and/or compounds and dust particles and H₂S, is connected to expansion turbine 2 with adherent generator 3 for power 20 generation and or mechanical or hyά auHc power transmission for operation of engine/machine - for example the air compressor 8. From expansion turbine 2 outgoing fuel gas/condensate mixture 39, now with condensate containing eariier vaporized agents and/or compounds and eariier gas carried dust particles, is connected to separation device 14 with return of this dust and vaporized agents and compounds containing condensate 32 to the preparing fuel stage 321, for example the evaporation plant, .and the reaction chamber 1 and subsequent melt dissolver/cooler 126A and 126B and for partial or total moisture saturation of the fuel gas 38, before and/or after fee sofid phase separation, in the whole or parts of. The gas phase 40 after separation device 14 is connected to fee second expansion cooHng stage 4 with adherent generator 5 for power 20 generation or another energy form. From expansion turbine 4 outgoing n ixed flow of fuel gas and condensate 41 is connected to device 15 for separation of clean, tempered condensate 33 suitable for district heating, pulp washing etc. Gas phase 42 after separation device 15 is connected to the third expansion cooling stage 6 with adherent generator 7 for power 20 generation or another energy form. This very last expansion cooHng stage 6 expands fee gas-/condensate rnixture 43, with H₂S content down to negative pressure/vacuum 0,05 bar (a) with corresponding temperature around 23°C by the present condensation effect strengthened with some form of negative pressure/vacuum generating equipment, as a whole or part of it, as Hquid ring pump 9 after separation device 1 , and barometric condensate faH leg with water-seal and vacuum pump 10 on condensate flow 34 to tank 19 wife feed out of expansion cooled, clean condensate 34 excess for reuse or to

cooled^'condensate 34 excess. After separation stage 17 for the cooling and sealing water 24 the gas phase 44, with content of H₂S, is passing fan 11 for feeding the fuel gas to the gas boiler 12 where the fuel gas 44 is combusted during oxidation of the H₂S-content to SO₂ together with the added "strong" gas — non condensable gas (NCG) 90. These gases are also connected to, one for the evaporation plant and the expansion cooHng common system for negative pressure/vacuum, at for example gas pipeline 44. The gas boiler 12 is preferably utilized for increasing the physical energy content of fee system by preheating the gas and/or condensate phases, before and/or after fee expansion stage as for example the gas-/condensate flow 39; alternatively for conventional steam production. After gas botier 12 the flue gas with SO₂ content is divided in two partial flows with connections to the SO₂-scrubbcr 104A and 1 4B. This can be preceded by a conventional process stage for the absorption of SO₂-gas in water. Whereupon the flue gas 45, now treated from SO₂, is led via gas fan 13 to funnel. There is a possibiHty to rnstafi a flue gas condenser 22 (missing in this figure) after the scrubbers. After the steam condensation of the flue gas there nearly only remains carbon dioxide (CO ) — besides fee nitrogen N₂-content when used compressed air 35 - with a possibiHty to be recovered and Hquefied for other markets or final waste disposal. Back to reaction vessel 1, the melt phases 18A and ISBB respectively of which, pass process stage for melt dissolving and cooHng 126A and 126B respectively -with Hquid addition by condensate 32 to pre decided concentration. Both these process stages 126A and 126B also settle the relation between fee amount of carbonate (Na₂CO₃) and bicarbonate (NaHCO₃) by the absorption of fee fine gas CO₂ content The carbonate solutions ISA and 18BB are pressure decreased by Hquid expander 80A and 80B wife or without adherent generators 81 A and 8 IB for power 20 generation. The subsequent liquid/gas phases 181 A and 18 IB pass the separation device 85A respective 85B with connection of fee expansion steam 180 to the eariier described separation device 15. The carbonate solutions 182A and 182B are after that fed to a mud/pressure filter 95A respective 95B for the removal of NPE 54A and NPE 54B respectively. The carbonate solution 182A also contains a certain amount of NaOH and is divided in two partial flows, when one is fed to the caustification plant 51 for production of nearly sulphide free NaOH 55. The other flow part is fed to scrubber 104A for absorption of the SO₂-content of fee flue gas and production of sulphite solution (Na₂SO₃) 183 A. The bicarbonate solution 182B Is fed to Sθ2-scrubber 104B for the production of bisulphite solution (NaHS0₃) 183B. The proportions of both sulphite flows have thus been pre decided eariier in the process in connection with the melt dissolving 126 A and 126B. The figure thus

there is no need for se arate flows, the proceeding can be simplified by means of only one gathered flow of carbonate bicarbonate which later can be transformed to sulphite/bisulphite by only one SO₂-scrubber stage. Further one proceeding - a quite simplified one - is the production of sulphite Na₂SO₃ via Na₂CO₅ NaOH-soIution 18 from only one melt dissolving stage 126.

The sulphite pulping processes, with base ofMz_* NH^ or Ca Besides the above described Na-based sulphite process there are further some sulphite processes withrother base chemicals ^"as magnesium (Mg), ammonium (NH₄) and calcium (Ca). Below foHows a comprehensive description with figure of respective base according to the present invention. GeneraUy the combustion of these sulphite waste liquors are based on total oxidation during the reaction progress during high process pressure, high steam partial pressure and when occurrence of sulphur fee sulphur content is recovered as SO₂ in the flue gas. Base chemical, or the rest of It is recovered as a phase of solid and/or molten material from the reaction progress and/or in the form of fine particular dust, fly ash, out with the gas phase. The gas carried fly ash is essentially transferred during fee first condensation/expansion cooling stage, accorάing to earlier description, to this first condensate flow. The amount of condensate is settled by the process pressure of the gas phase, steam partial pressure and the outlet/counter pressure of the expansion cooling stage. After this gas cleaning stage mainly concerning the dust content, the Sθ2-contcnt of the flue gas remains, which principaHy Is absorbed by the actual process base chemical in an ending SO₂ -scrubber stage to actual sulphite cooking chemicals.

Figure 19:

This proceeding comprises fee combustion of magnesium based (Mg) waste liquor during total oxidation for fee production of magnesium sulphite (MgSO ) and/or magnesium bisulphite [MgfHSO^] as sulphite cooking acid During the reaction progress, temperature

around 900-950°C, magnesium oxide (MgO) is formed as fly ash and the sulphur content as S0₂ — with all of It in fee gas phase. By controHed stoichiometry during the combustion process almost prevents the formation of magnesium sulphate (MgSO₄) and SO₃. The earlier gas carried MgO-ash passes during the first expansion cooling stage to the hot Hquid phase when MgO is transformed by slaking to magnesium hydroxide [Mg(OH)₂3 according to: MgO +H_?O ^ Mg(OH In order to secure the reaction fully, normally a certain retention time is required - preferably as here in a pressurized system. Flue gas with among others SO₂-content passes another expansion cooling stage down to negative pressure/vacuum, preferably within fee area 0,05 — 0,50 bar (a) depending on how the clean condensate excess is utilized. After this the flue gas is fed to a scrubber system, atmospheric or pressurized, for the absorption of the SO₂-content during the conditions of fee present cooking method according to: Mg(OH)₂ + 2SO₂ <<= Mg(HSO₃)₂ . ^•M (HSO₃)₂ ^^"Mg(OH)₂-^-2M Sθ₃ + 2H₂θ ^" - The eariier mentioned negative pressure/vacuum is produced, besides by the condensation effect among others preferably by fee Hquid ring pump which cold water supply as cooHng and sealing water also comprises gas washing with regard to fee content of hydrogen chloride in the gas - feus a form of chloride separation. Sulphite waste liquor with water content 30/31, is thus connected to reaction chamber 1 together wife magnesium sulphate (MgSO₄) or magnetite (MgCO₃) as Mg-refill 110 and petroleum coke 103 as S-refiU and fuel addition together wife recycled condensate 33 for stoichiometric combustion/total oxidation by means of compressed air 35 as an oxldant with addition of other oxygen containing substances as O₂ 36, H₂O₂ 37 or O₃ -rest 115 (sometimes wife traces of CO) from fee bleach plant as a whole or parts of it From fee reaction chamber 1 outgoing flue gas 38, superheated or during partial or total moisture saturation, is fed to a first expansion cooling stage 2 interconnected with turbo compressor 8, generator 3 for power generation 20 and with start up motor 83 if generator 3 misses starting up function/reversing. After expansion turbine 2 the outgoing flue gas/condensate flow 39 is fed to separation device 14. The condensate flow 32 with the content of recovered MgO, fully or partly transformed/slaked to Mg(OH)₂ passes a Hquid expander stage 80 wife or without electric generator 81 whereupon the Hquid-/gas mixture is connected to separation device 85 for gathering of MgO- Mg(OH)₂-Hquid phase in tank 113 - at ospheric or pressurized. Into this tank MgO 112 Is added, if required, as an alternative refill. The outgoing flow of Mg(OHh 114 is fed to a scrubber system 104 for absorption, during pH-control. of fee flue gas S0₂-content. From scrubber 104 the sulphite cooking acid 108 is equipped wife fee possibility of recirculation 108A. After scrubber 104^' the flue gas 45A is fed via fan 13 to a funnel. Back to the separation device 14 and outgoing flue gas 40 which is connected to the second expansion cooHng stage 4 with adherent generator 5 for power 20 generation or another form of energy. After fee expander turbine stage 4 the

separation device 85. After separation device 15 fee condensate fraction 33 is fed via vacuum pump 10 with or without barometric condensate f H leg wife water-seal to the condensate tank 19 wife recirculation of condensate 33 to reaction chamber 1 wife the possibiHty to intermittent condensate flushing 33A when required according to dashed line. The condensate 34 excess from cistern 19 is used for pulp washing 99 or for another purpose — for example district heating 23. The outlefc^/counter pressure of the last expansion cooling stage 4 settles fee temperature, according to earlier described, if re-use is of interest or if fee water excess goes to recipient After the separation device 15 the gas fraction 44, containing SO , is fed via

water 24, which also comprises gas washing according to earlier description. After fee separation device 17 and fan 11 the gas fraction 45 is led to eariier mentioned SO₂ scrubber 104 whereupon fee flue gas 45 leaves fee proceeding via fan 13.

Figure 20: The present figure exemplifies the invention by means of combustion of ammonium sulphite waste Hquor [( H₄.)2 SQs] during total oxidation further forming one process variant with the combustion products almost only gaseous during well controUed stoichiometry, among others in order to avoid acid adhesive substances. EssentiaHy SO₂ is recovered from .fee cooking chemicals but also a smafi amount of ammo urn/ammoniac (NH /NH₃). The combustion of ammonium/arnmoniac gives nitrogen (N₂) and a big amount of water/steam according to: 2NH₄ + 2O₂ <=> N₂ + 4 H₂O After fee reaction progress the flue gas contains a small amount of fine particular dust originating from he wood raw material as potassium (K), sodium (Na), magnesium (Mg) and siHcone (Si) which is separated in full or partly direct after the reaction progress or after fee expansion cooling stage, preferably after the first expansion stage, which comprises a second separation stage, mainly the most fine particular dust fraction, which feus is recovered in the condensate according to eariier description. Further fine particular dust originating from the reaction progress constitutes of ammonium salts which In the corresponding way is recovered in fee condensate. The equiHbrinm of the alkaline content Is strongly influenced by the process pressure during the reaction progress according to:

An increased reaction pressure thus displaces the equilibrium towards fee left. A more condensate phase after fee first expaasϊoj cooling stage, containing as well NH as H₃₃ 1& brought back partly to fee reaction progress and partly to the absorption stage for utilization of the SO₂-content of fee flue gas by generation of renewed ammonium sulphite solution [(NB .)2 SO₃]. As not all fee ammonium is recovered refill is required in the form of fresh ammoniac (NH₃) to fee absorption stage. The system for the recovery of fee whole ammonium sulphite solution can as an advantage be performed pressurized. The chloride separation of the system is done by washing out the hydrogen chlorine content of the gas phase by cold watemr cooHng and sealing water 24 for fee liquid ring pump 9. The ammonium sulphite waste Hquor 30, according to above, with water content 31 is feus connected to reaction chamber 1 together with external condensate containing axrunorήun arnmoniac 120, recycled condensate 32A and petroleum coke 103, being S-refiH and fuel addition (option), in full or parts of i for stoichiometric combustion/total oxidation by compressed air 35 as oxidizing agent Dust particles originating from fee reaction progress and fee wood raw material are separated together with a small amount of slag etc through a smaH separation flow 18A and when required also 18B, From the reaction chamber 1 outgoing flue gas 38, superheated or during partial or total moisture saturation, with fee content of as weH SO as some NH₃ is fed to a first expansion turbine cooHng stage 2 connected to turbo compressor 8 and generator 3 for power 20 generation and start up motor 83. After expansion turbine 2 fee outgoing flue gas/condensate flow 39 is fed to separation device 14. The condensate fraction 32A and 32B, now contϊrining the eariier gas carried fine particular dust is brought back to reaction chamber 1 by condensate 32A and with a small flow to separation/cooling equipment for slag, melt etc 18 A, while fee fraction 32B is fed to SO₂-scrubber 104. The later process stage can be carried out pressurized or nearly atmospheric according to figure. The condensate flow 32B is pressure reduced according to requirements through pressure reducing valve, alternatively through a Hquid expander stage (not shown in figure). Fresh ammoniac (NH₃) 121 being a refill is added to fee scrubber system 104 for SO₂-absorption and further production of ammomum sulphite cooking acid 108 with recfrcuiatlon flow 108 according to requirements. Back to separation device 14 and separated flue gas 40, with content of SO₂ and a small amount of -NfH₃, fee flue gas is connected to next expansion turbine cooHng stage 4 wife adherent generator 5 for power 20 generation or another form of energy According to earlier process descriptions/figures, fee outlet counter pressure after fee last expansion cooling stage settles the final temperature of

Moreover in this figure the same arrangement is shown with Hquid ring pump 9 and vacuum pump 10 etc corresponding to earlier figure descriptions-

Figure 21: The proceeding according to the present figure comprises as a principle the original, now closed down sulphite pulping process, based on calcium (Ca). This proceeding is fee last exemplification of fee sulphite pulping process within fee present invention. The combustion ^" of ΕEe sulpHite waste Hquor

controUed stoichiometry and reaction temperature wife only gas bounded recovered chemicals as a consequence. Quite decisive is that the calcium base is recovered in the form of calcium oxide (CaO) which requires a temperature above 1150-1200°C during the reaction progress, while fee sulphur is recovered as sulphur dioxide (SO₂)- The fine particular calcium oxide dust (CaO) is transformed by slaking to calcium hydroxide [C ^H ] , in one or more stages, the one in a pressurized quench direct after fee reaction progress and fee other stage in a later process stage. Commonly for both stages is that fee CaO-dust is slaked with water according to: CaO + H₂O <^> Ca(OH)₂ Whereupon the calcium hydroxide [CatOH ] is carbonized by fee flue gas carbon dioxide content (CO₂) to calcium bicarbonate [Ca(HCO₃)₂] according to:

Ca(OH)₂ + CO₂ o Ca(HCO₃)₂ The carbonizing continues in parallel wife fee slaking as a first stage in quench 12 A direct after the reaction chamber with the second stage — atmospheric or pressurized — as a mufti functional apparatus 126B (figure 22) after the first expansion cooHng stage wife fee foHowing extent: • Separation gas/condensate flows * Trar-sformatiorr/slaking of CaO * Addition refiH of fresh "substance^'", for example CaO or Ca(OH)₂ • Carbonizing Whereupon the calcium bicarbonate flow is fed to absorption tower/scrubber for absorption of the flue gas SO₂.-cont.ent for fee production of calcium bisulphite [Ca(HSO₃) ] as cooking

acid liquid according to: CaCHCO₃)2 + 2SO2 CaCHSO3)2 + 2C0₂ Calcium is only dissolvable in bisulphite form and belo pH 2,3. Calcium sulphite waste Hquor 30 according to above wife water content 31 is feus connected to reaction chamber 1 togefeer with S-refill 103 in fee form of petroleum coke (3-4% S) and or as sulphur S, and/or calcium sulphate CaSO and recovered condensate 33. From reaction chamber 1 outgoing flue gas 38 with content of CaO-dust and SO₂, superheated or during partial or total moisture saturation, is connected to a first expansion cooling stage 2 connected to turbo compressor 8 and generator 3 for power 20 generation or another energy form. After expander 2 fee outgoing flue gas / condensate π-lxture 39 wife the content of CaO/Ca(HCO₃)₂ is fed to separation device 126B with further functions as slaking and carbonizing. The calcium bicarbonate solution 127 prepared by the multifunction stage 126B is fed to scrubber 104 for the absorption of the flue gas SO₂-content and fee production of calcium bisulphite solution 108 with possfeϊHty to recirculation 108 A. Whereupon fee flue gas 45 is fed via fan 13 to funnel- According to earlier figure descriptions fee outlet/counter pressure of fee last cooling, turbine expansion stage settles fee temperature of fee gas condensate fluid. When needed a greater negative pressure/vacuum, besides 1he condensation effect among others created by liquid ring pump 9, there is a possibiHty of Hquid ring pump operation by connection wife, for example, fee last expander turbine stage in fee <κ>rresρonάιng way as the turbo compressor 8 at the first expander turbine stage 2.

Figure 22:

The present invention feus also comprises a multi. functional apparatus 126A/126B according to this figure with a number of different process possibilities according to the conceptual circumstances:

• Separation of gas-Zfiquid-phases • Gas moistening before and/or after fee smelt separation • Smelt dissolver/quench

» Carbonizing of ''substance^*' in for example hydroxide form by the gas CO₂-content • When appropriate avoiding fee

effect • RefiH of fresh "substance^w in for example carbonate, oxide or hydroxide form • Addition 40N of ammoniac NH₃ and/or urea (NH₂)₂CO in order to chemically reshape nitrogen oxide NO^ to nitrogen N₂ and steam The site of fee multi functional apparatus of fee proceeding is either direct after the chamber reaction progress and or direct after the discharge of fee first expander cooling turbine. The apparatus, preferably pressurized consists of a system of concentricaHy designed intermediate waHs 125 creating a form of multi stage Hquid-lock for fee best stirring wife fee best contact between gas phase 40 and fee Hquid phase 127 with fee possibility to supply "substance" as 18, 112 as weH as 40N direct into fee stirring zone. The bottom part of fee intermediate walls 125 are carried out with saw-toothed design 125 B forfe .best flow distribution aH around the turns.

The τniesration of the sulphite pulping process

The sulphite pulping process with its different "bases" has earfier been described according to sections and figures 18-22. By fee present invention, the possibiHty of direct conversion of among others Na-based cooking chemicals is thus presented - consequently without fee extensive and expensive separatioh spHt of alkaH metals and sulphur compounds. The ultimate energy and chemical recovery occurs at integration of these sulphite pulping processes. Below foHow figures 23 and 24 showing direct production of sodium sulphite ( a₂SO₃) and or sodium bisulphite (NaHSO₃) - all according to fee process requirements

Figure 23:

Separate process details have earfier been described under The sulphite pulping process with base ofNa and by Figure 18, why this figure gives a more overall description. Sulphite waste Hquor 30/31 thus connects evaporation plant 93 togefeer wife flow 321 constituting all or parts of fee condensate flow 32 from fee first expansion cooHng stage wife content of condensed agents/substances and compounds. From fee evaporation plant 93 leaving flows consist of besides thickened spent liquor 30/31 also of a smaU condensate flow 120 containing a large part of fee occurring condensed volatile agents/substances and compounds which together connect the reaction chamber 1. The vacuum system of fee evaporation plant for non condensable gases NCG 90 is co-ordinated wife the corresponding system of the expansion cellin -^*fOT Ex^^ progress of fee reactiorj chamber 1 is characterized by distributing sulphur (S) with fee fuel gas as H₂S and sodium (Na) wife fee melt fraction as a solution of NaOH and Na₂CO₃, alternatively as only Na2CO₃ and/or NaHCO₃ by means of piping 182. These Na-compounds absorb by fee gas boher 12 oxidized. H₂S to SO2 by a subsequent SO₂ absorption stage 104 when the Cθ2-amount leaves the carbonate compounds via the flue gas 45. This is preferably preceded by a conventional process stage for absorption of SO₂ in water. The sulphite solution 183 in fee form of Na₂SO₃ and/or NaHSO? has by feat get ready. Segregated condensate recovery is obtained by means of hot and contaminated condensate 32, which is returned -tempered^ clean and CO₂-containing-condensate -33-is-suitable for example pulp washing and fee expansion cooled, clean condensate excess 34 for any kind of re-use or to recipient This condensate recovery/segregation— ithout any cooling water need — is a strong contribution to fee present efficient and closed, recovery process. Steam 89, preferably as high pressure, is produced by means of feed water 88 via gas boiler 12. Power generation 20 by a triple stage turbine expansion cooHng procedure, expanders wife adherent generators 2/3, 4/5 and 6/7 respectively, alternatively by expander turbine operation of another engine as compressor 8.

Figure 24: Within fee present figure a number of separate process details have been described earfier, mainly under section above, figure 23. What is made clear by fee present figure 24 is fee extensive integration by the S-/Na-sρHt of the reaction progress 1, fee segregated condensate recovery and the flow exchanges with fee evaporation plant 93 comprising fee NCG-system 90, gas boiler 12 wife preheating of dirty, segregated evaporation condensate 120 before connection to fee reaction chamber 1 and fee production of steam 89 for among others the evaporation plant 93. Clean condensate 151 from, the evaporation plant is connected to the corresponding condensate flow from fee turbine expansion cooHng stage 4. After gas botier 12 foUows an SC^-absorption stage 104 by alkali solution 182 constitutes a nearly sulphide free green liquor NaOH + Na₂CO₃- This is preferably preceded by a conventional process stage for absorption of SO₂ in water (can not be find in the figure). After fee Sθ2-absorption stage — comprising the necessary separation of the carbonate CO₂~content— fee completed sulphite solution Na₂S0₃ 183 is obtained. The integration also comprises causticising 51 of a partial flow of nearly sulphide free green Hquor 182 for the production of nearly sulphide free NaOH 55 mainly for bleaching plant 87A, fee effluent 87 of which is connected to evaporation plant 93. Below there are some sections, which deal with essential — generally -valid -process conditions within the present invention:

The steam partial pressure The energy parts of fee gas phase consist of: • The chemical energy The part of chemical energy comprises fee fuel value of fee gas, mainly from fee gas parts of CO, H₂, CH₄ and H₂S, expressed as efficient heat value kJ/Nm³ dry gas,

• The physical energy The part of physical energy comprises gas pressure, temperature (sensible heat), evaporation/condensation (latent heat) and when there is a melt also wife addition of chemical (fessolving heat) and physical heat

The energy parts above are distributed by the operation criteria of fee reaction progress — essentiaHy by fee steam partial pressure. Increased steam partial pressure gives fee corresponding increased part of physical energy into fee gas phase at the cost of fee part of chemical energy. The steam partial pressure influences also fee reaction progress in full, from fee very first start of fee progress to its ending phase. The latter comprises fee very important and sensitive end oxidation of the remaining char/heavy hydrocarbon compounds, fee steam reforrning of which is in direct proportion to fee steam partial pressure. The high steam partial pressure can also make possible an interesting energy contribution to the reaction progress in the form of natural gas/methane (CH₄) as for example afomization agent with endofeermic equOibrium reaction according to:

The equifibrium is displaced towards fee right by the (water) steam. The principle also aUows production of synthesis gas (CO + H₂) out of natural gas as a raw material during simultaneous gas cleaning and energy recovering in the form of power generation alternatively mechanic or hydrauHc operation of engine. Increased steam partial pressure increases naturally fee steam amount/volume. Necessary apparatus volume Is however more than enough compensated for by fee preferably increased process pressure. Ηte chloride separation When there are chlorides into the fuel in connection wife energy and chemical recovery and especially when closing a system/cycle, it is a condition feat fee chlorides continuously are separated out of fee system in order to prevent chlorides building-up. There is a possibility, when combustion, preferably during total oxidation, of a fuel wife content of sulphur compound and chlorides (NaCl/KCl) to transform these chlorides to hydrogen chloride (HCl), when sulphur dioxide (SO ) present which facilitates the transfoπnation, whereupon -chlorides are separated in the-form-of HCFvia hydrochloric acid-scrubbers or-correspondingly. These circumstances are essentially appHcable within some of fee sulphite pulping processes - for example when utilizing the chloride rich fly ash (Na₂SO₄) of the sulphate iH - wife the chemical recovery of among others sulphur in oxidized form as sulphur dioxide (SO₂), whereupon the chloride separation takes place in the form of hydrogen chloride, which is dissolved in the following cold water scrubber, Hquid ring pump 9 or correspondingly to hydrochloric acid (HCl).

The carbon conversion

The principal control function of the oxidation progress is most often the remaining part of char and/or hydrocarbon compounds. Partial oxidation — feus gasification — means increased difficulty to achieve necessary, nearly one hundred percent carbon conversion. Increased steam partial pressure is quite decisive for the possibility to achieve fee requirement of fee carbon conversion degree. Steam gasification or steam reforming reduces fee partial pressure of fee hydrocarbon compounds when processes that lead to carbon/char formation are counteracted. Steam gasification of char is for example 3-4 times faster than fee coiresponding oxidation potential of carbon dioxide (CO ). The strong importance of fee steam can be seen in fee equilibrium reactions below. Increased steam partial pressure (H₂0) displaces fee equIHbrium towards fee right and fee potential driving force increases in proportion to fee increased steam partial pressure.-The operating conditions make possible as an almost pure water gas reaction: ■ The maximum carbon conversion: 3C + 2H₂0 o 2CO + CH4 ^■ The surnmation reaction of the carbon conversion: 2C ÷H₂0 ÷ 0₂ <^> CO + CΘ2 +H2 ^" rSim

^' CO -÷ χp^',Sϊά ÷n) i M r^~ ■ The steam reforming:

■ The water gas reaction: C ÷H₂0 > CO +H₂ ■ The water gas equifibrium: CO +S2O «- CO₂ + H₂ Regarding fee waste Hquors of fee pulping industry and for example the black Hquor of fee sulphate pulping process fee content of sodium and-sulphur compounds forms-a-phase of solid and/or molten material at temperatures above fee area 760 - 800°C. When a chosen temperature margin of around 100°C above said temperature area, an almost optimal reaction process can be made according to the present proceeding during almost complete carbon conversion - thus above 99,5% - thanks to fee favourable steam partial pressure with the said improved end char oxidation. In this way the temperature level of fee reaction progress can be restrained to fee area of 880 - 920°C.

The equilibrium reactions oftlie reaction progress regarding alkali/sulphur split The pulping industry has since a great number of years an unsatisfied requkement from fee research and development side, when recovering chemicals and energy from the waste Hquors, regarding fee need for spfit of alkaH and sulphur compounds as separate flows. The spHt should be almost total. It has feus surprisingly turned out feat according to fee present invention, a certain combination of process criteria during fee reaction progress — according to below— akes total optimization possible of as weU fee fibre process as the chemical and energy recovery in fee form of among others high degree of sulphate reduction, high degree of Na-/S-spbt and lower total steam consumption and almost without any need for cooling water with subsequent considerably higher efficiency of power generation, or another energy form, thanks to essentiafiy lower exergi losses. The principal equIHbriurn reaction for fee allsahVsulphur separation— fee spHt - constitutes by: Na₂CO₃ -i-H₂S <= Na₂S +H₂O + CO₂

The equIHbriurn displacement towards fee left is almost total by fee below process criteria during fee reaction progress - feus fee sulphur is driven out wife fee gas phase in fee form of hydrogen sulphide (H₂S), when a carbonate melt (Na₂CO₃) remains almost completely free ~^m ύlp E3e^"(. ₂S ^" ihe^'ϋarrκmateTneϊt can of sodium - hydroxide (NaOH): • High process pressure • High steam partial pressure • The lowest possible temperature during fee reaction progress, from the carbon conversion point of view- Char is oxidized, besides by oxygen and steam, also by carbon dioxide (CO₂) which in this respect is in opposition to hydrogen (H₂) and carbon monoxide (CO). • Recycling of carbon dioxide to the reaction progress. • Hi gEer ^"b ygen-/fuel ^"ratio gives bigger arhounfof carbon άToxϊα'e^'at ffie cost of fee amount of oxidation restraining hydrogen and carbon monoxide. • The energy recovery of fee expansion cooling turbine is favoured by fee great part of physical energy in fee gas phase, esscntiaHy in fee form of pressure, temperature and condensation heat — fee latter as a result of fee high steam partial pressure.

It can be noted feat at causticising of nearly sulphide free green Hquor, the white Hquor preparation is influenced positively by fee fact feat the causticising degree wiU be higher, when the ion strength relation is changed positively. Table below shows the distribution of Na-/S-compounds — so caUed spfit — at different operation criteria during fee reaction progress as steam partial pressure (Gas vol. -%H 0) and temperatures (°C) and pressure conditions (bar α). The content of Na-/S-compounds of fee melt (Melt weight- %) can be seen together wife a summary of the S-content of the melt (Sum. S weight- %), The amount of physical energy of fee outgoing gas phase can also be seen (Phys. in gas out %). As a reference ( "Ref. 33 "J fee operation criteria of fee combi concept/integrated combined cycle concept (ΪGCC) have been chosen with DS-content 75%, operation pressure 33 bar (a), operation temperature 950°C which gives fee amount of S in the melt phase as Na₂S being 11,57 weight-%.The possibility to split at fee present invention can be seen in this table wife fee amount of S in fee melt phase, as Na₂S, of only 0,57 - 0,90 weight-% within fee temperature and pressure area of fee reaction process 880-920°C and 150-200 bar (a) respectively. According to reference ("Ref 33") fee gasification criteria of fee combi concept and experiences done, the low temperature area of 880-920°C is quite impossible in order to among others achieve a necessary carbon conversion degree.

Table below wife fee Na-/S-spfit at different operation conditions during fee reaction progress: • The reference (*Rfft 33"): Black Hquor of DS-content 75% without any content of sulphate soap, operation pressure 33 bar (a), temperature 950°C, oxidizing agent of 90 % O₂. * The present invention: Black Hquor of DS-content 40% wife remaining sulphate soap, oxidizing agent of 90 % O₂. Different operation criteria according to table below:

- Reaction pressure 100-200 bar (a)

The xidizing agents The present invention does not allow only oxygen containing gas as an oxidizing agent but also "oxygen containing Hquid" —for example hydrogen peroxide solution (H₂O₂). Hydrogen peroxide has a large feermodynamic energy content which means that large amounts of energy are released at its decomposition during fee reaction progress and give besides oxygen also valuable steam as rest products according to the decomposition reaction below, which further increases fee steam partial pressure and by that also the valuable part of physical energy into the gas phase. - " ' — 2H₂O₂ o O₂ + 2H₂O The decomposition reaction, according to above, occurs rapidly and is exothermal. It is catalysed by fee contact of the progress with alkaH compounds, organic substance, heavy metals and high temperature. Besides feat fee decomposition reaction is favoured by fee extraordinary big contact surface by the atornization of fee fuel into small droplets, preferably within sizes 50μ - 0,50 mm- The concentration of the hydrogen peroxide solution— usually 30-90 % content of H₂Q2 — influences fee intensity of fee reaction progress as weH as the steam partial pressure. The production of hydrogen peroxide on-site of fuel gas from gasification of pulp waste Hquors, to be utilized as a bleaching agent for pulp products, is earfier known from patent document SE 93 / 00778. Through fee process design described by the present invention it is also possible to produce hydrogen peroxide on-site from hydrogen sulphide H₂S and to utilize ihe hydrogen peroxide as an oxidizing agent during fee reaction progress. An mteτest g utilization of fee decomposition reaction of the peroxide during the reaction progress is, in full or partly, to achieve necessary operation pressure during fee reaction progress by fee hydrogen peroxide addition. Further one reactive, possible oxidizing agent is ozone (O₃).

The fuels/raw materials

Suitable fuels and raw materials within fee present invention are exempHfied according to below: • Pefroleum-reste-/-fractions/-coke, crude oil, heavy sulphur rich oil, heavy oil, waste ofi, dlesel ofi, paraffin « Coal, coke, bitumen - Hydrogen (H₂), mercaptan, NCG, hydrogen compounds as for example hydrogen

» RefiU: sulphur (S), hydrogen sulphide (H₂S), green hquor mud, sulphate soap, tall ofi, sodium sulphate/fly ashNa₂SO₄ • Alcohols, ether compounds (as DME), turpentine, esters « Household refuses, slaughter house refuses/animal rest products, cremation * Bio fuels/renewable fuels: * Waste Hquors within the pulping industry: Sulphate pulp, Sulphite pulp, NSSC, "Cross recovery" Cltemi-/m"echariical pulp, CTMP * Safix, micro algae, bark, logging waste, saw mill rests * Bio mud, digested sludge (also containing CHj-rest), molasses, olive seeds, vegetable ofis and grease, biogas * Peat one-year plants/field crops including seeds/straw fuels

The energy distribution The proceeding according to fee present invention is mainly based on fee evaporation during the reaction progress essentiaUy of water, during considerable energy absorption in fee reaction chamber with subsequent steam condensation, during corresponding energy ermtting at expansion cooHng in at least one stage during at least one partial stage of some type of expansion cooHng turbines, wife both progresses acting direct without any effectiveness/efficiency restrictive influences of heat exchanger surfaces, and in principle quite without any cooling water consumption. The total isentxopic efficiency of fee proceeding is also very high by fee rechcnlation of high temperature condensate/s and above all at multistage expansion cooling- In this way fee amount of exergy losses is minimized substantiaUy, with for example when given priority to power generation, at very high -value — thus fee ratio between produced power and fee heat The energy distribution between power generated and produced heat is governed by fee total/overall recovery need and by feat the process elaboration as combustion under partial and/or total oxidation as weU as fee number of stages during fee reaction progress, and further fee number of expansion cooHng stages/partial stages wife chosen outlet counter pressure and by feat also the outlet temperature and the distribution of respective amount of condensates — a segregated condensate recovery.

level of the final fraction of fee condensate — feus a cooled and clean water for re-utilization or to be fed to fee recipient. At fee later case it is suitable wife expansion cooHng down to temperature around 20°C. A furfeer carrying out is a condensate integration with some type of heat pump arrangement when especially fee last condensate fraction is utilized for the mentioned arrangement wife for example expander turbine operation of fee heat pump compressor.

The energy distribution wife for example combustion during total oxidation of essentiaHy dry ^"deHvered fuel wife turbo compressed air as an oxidizing agent and recirculation of fee condensate flow/s between fee evaporation and condensation sequences, fee energy distribution when given priority to power generation is calculated to:

• Power/electricity production 70-72 % • Losses o Electricity consumption (not recovered energy) 6 % o Various heat losses 14 % o Unbalance in fee amount of recycled condensate - thus excess/deficiency 8-10 %

When combustion during total and/or partial oxidation of wet deHvered fuel wife turbo compressed air as an oxidizing agent a somewhat larger unbalance arises wife fee corresponding excess in fee condensate handling and according to feat somewhat higher exergy losses as a consequence, mainly depending on fee amount of water in fee fuel, type of oxidation progress and fee conditions for fee condensate re-utilization. The calculated energy distribution when given priority to power generation is:

• Power/electricity production 68-70 % • Losses o Electricity consumption (not recovered energy) 6 % o Various heat losses 14 % o Unbalance/excess in fee amount of produced condensate in relation to fee recycled amo unt 10-12 % Comments to the extent • By fee raw material of the pulping industry, comprising wood chips, among others potassium (K), sodium (Na) and sulphur (S) are added to fee chemical cycle. « When alkaH metals or sodium compounds are described, it must also be understood feat potassium compounds wfll come naturally according to above, • The invention also comprises so caUed "sulphur free" pulping processes, mcluding fee soda process - however wife fee exception that sulphur is not added in another way than above. • The invention is also appHcable on so called "causticising free" recovery processes as for example at utilizing of titanate, treatment of sulphide free green Hquor with ferrite or boron addition which reduces the oeεd of causticising. • Regarding fee expander turbine or the corresponding arrangement of the expansion cooling stage, it must be understood feat fee added gas is moisture saturated or partiaHy moisture saturated— fee latter corresponding to somewhat super heated. • It must be understood feat the name combustion/thermal decomposition comprises as weU total oxidation as partial oxidation. The latter is understoichiometric combustion - thus synonymous wife gasification. • It must be understood feat during certain cHcumstances fee oxidation progress will occur without any real flame. • It must be understood feat in certain parts similar wording in earlier known, published documents regarding understoichiometric combustion — a reducing process — differs essentiaHy from an apparently similar wording in fee present invention which in certain parts describes stoichiometric combustion — an oxidizing process.

Claims

PATENT CLAIMS

1. Method for recovering energy and when appropriate also chemicals, fee recovery of said chemicals comprising part or parts of phase of sofid and/or molten material, sub- /mlcroscopic and visual dust particles, in gaseous state or in aqueous form, from a fuel comprising apart or parts of: hydrogen, hydrocarbons and hydrogen compounds, by combustion thermal decomposition during partial and/or total oxidation, feus

at least one reaction chamber during at least one reaction progress within a pressure Interval of 2 - 220 bar (a) and a temperature interval of 600 - 3100°C, whereupon produced gas, superheated or during partial or total moisture saturation, with content of chemical and/or physical energy is cooled by condensation of into said gas vaporized agents and/or compounds, c h ar a c h t e r i z e d i n feat fee condensation takes place by expansion cooHng through at least one expansion turbine (2, 4, 6) during at least one partial step or by sinfilar apparatus wife corresponding functioning, when from fee oxidation progress of reaction fee chamber (1) originating gas carried sub-Zmicroscopic and visual dust particles, comprising fumes, are wetted during fee condensation, when said dust particles constitute condensation nuclei for fee vaporized, condensable agents and/or compounds, whereby fee weight of said dust particles is increased and said dust particles fall out of fee gas phase (38) with transfer into fee liquid/condensate phase, which phases are separated by at least one separation device (14, 15, 16) simultaneously when the gas phase contains chemical energy, said energy is utilized for production of chemicals and/or energy (20, 89), whHe fee gas content of physical energy during fee expansion cooling is converted into (electric) power (20) by at least one expander turbine connected power generator (3, 5, 7) and/or converted by at least one expander turbine for driving at least one stationary machine (8, 82) or for driving a roobfie machine/engine (83 A), while furfeer chemicals are recovered as at least one phase of preferably solid and/or molten material and or as said dust particles and/or in gaseous state and/or in aqueous form, when preferably said sofid phase is separated by at least one quench (18) to be resolved, when appropriate, into at least one water containing medium (32, 94) by said quench and/or by at least one melt dissolver (126) as at least one aqueous product while said dust particles mainly are transferred into the Hquid phase by the condensation progress during fee expansion cooling, whfie fee gas flow containing gaseous components, suitable for recovering, said device ^'(61-64^', 5i-9 jlor^"the production of apart or parts of: phase of sofid and/or molten material (58, 69), gas phase (68, 45A-45B) and liquid phase (37, 55 A, 108, 183) wife return of within the method recovered chemicals, as a whole or parts thereof, and/or to be brought out of fee method.

2. Method according to Claim 1, c h ara ct eri z e d i n feat fee condensation comprises water/steam and when appropriate also other condensable agents and/or compounds as volatiHzable chemicals, volatilizable organic agents and or compounds and volatilizable none process elements (NPE)/heavy metals and/or metals.

3. Method according to any of Claims 1 - 2, c har a c t e r i z e d in feat fee steam partial pressure of fee reaction progress into fee reaction chamber (1) is at least equivalent to through oxidizing agent ato ization agent andor fuel (30) oxidation equivalence of provided amount of hydrogen, and/or fee steam partial pressure is increased equal to the reaction progress supplied amount of water containing agents comprising said fuel included amount of water (31) and/or to said fuel added amount of water and/or direct to fee reaction progress added amount of water and/or steam, said added water comprising preferably from fee expansion cooHng returned condensate and more preferably from a first expansion turbine step (2) returned condensate (32), as a whole or a part thereof, containing eariier gas carried sub-/microscopic and visual dust particles comprising fumes and/or earlier evaporated agents and or compounds.

4. Method according to any of fee preceding claims, c h ar a c t eri z e d i n that condensate returned from fee expansion cooHng progress is connected to at least one previous process step for pre treatment (321) of the fuel (31) before fee reaction chamber (ϊ) and/or when appropriate connection of said condensate to at least one quench (1 ) after fee reaction progress and or at least one process step for after-treatment (126) for recovering at least one phase of soHd and/or molten material in preferably aqueous form and/or wife fee connection of said condensate to at least one gas phase (38) for partial or total moisture saturation of said gas phase before and or after separation of said phase of sotid and/or molten material.

5. Method according to any of the preceding claims, c h ar a c t e r i z e d i n feat the operation pressure after fee reaction progress is graduaUy reduced by the expansion cooHng progress, resulting in segregated recovery of condensates by multi stage expansion cooHng with respect to cleanness, flow amount, pressure and temperature of said condensates, depending on discharge-Zcounter pressure of respective expansion cooHng step, down to suitable level of said pressure according to furfeer requirements of fee recovery, when final step of the expansion cooling preferably takes place - downto-about atmospherie pressure, more preferably down to negative pressure/vacuum and most preferably extended down to fee interval of 0,02 - 0,20 bar (a), when the gas/condensate flow after completed expansion cooling, at for example the discharge-/counter pressure of 0,03 bar (a) corresponds to a temperature of 18 - 20°C equivalent to extended energy recovering by the expansion cooHng turbine, wife or without a foUowing integration of any kind of heat pump proceeding depending on existing requirements of fee recovery.

6. Method according to any of fee preceding claims, c h a r a c t e r i z e d i n feat fuel atomization agents of the burner system of fee reaction chamber consist of hydrogen and/or gaseous hydrogen compounds and/or hydrocarbon compounds or oxygen containing gas or combinations hereof, preferably during partial or total moisture saturation of said atomization agents by water containing agents, more preferably steam and/or hydrogen peroxide H2O₂.

7. Method according to any of fee preceding claims, c har a c ter i z e d i n ϋxat oxidation agents of fee reaction progress consist of oxygen containing gas and or oxygen contairnfig Hquid fee oxygen containing Hquid preferably represented by a solution of hydrogen peroxide H₂O₂, preferably by simultaneously pressurizing said reaction progress of fee reaction chamber by decomposition reactions of said solution of hydrogen peroxide, as a whole or part thereof.

8. Method according to any of preceding claims, c h ar a ct e r i z e d i n that equilibrium and decomposition reactions of the reaction progress, with or without any additives as activators/catalytic agents, takes place during total oxidation of the fuel, preferably by pressurizing said reaction progress by reactions

c-emp sing-a JBa≤^»ϊ es^sentially free from carbon C and hydrocarbon compounds, said additives comprising a part or parts of: turbo compressed air and/or oxygen O₂, hydrogen peroxide H₂O₂, hydrogen H₂ and ozone O₃, wife an alternative possibHity to initiate a certain amount of said ozone direct into said air/oxygen flow by any kind of known method as for instance supplying electrical energy and or ultraviolet fight radiation into said air/oxygen flow, wife further possibiHty to integrate a fuel ceU process (122), preferably pressurized, whereby after completed expansion cooling by expander turbine and preferably for driving of any kind of mobile machine (83A), comprising railway, vehicle, shipping, submarine and aircraft, discharge of rest product only consists of clean condensate -whenusing-compressed air said discharge also comprises inert nitrogen N₂.

9. Method according to any of the preceding claims, c h ar a c te ri z e d i n that after completed expansion cooling the gas phase consists of nearly only carbon dioxide CO2, when appropriate for recovering in form of a part of said carbon dioxide (45 A) to be recycled into fee reaction progress constituting a part of the oxidation agents, as an outer cycle, while fee rest part of said carbon dioxide (45B) is brought out and preferably Hquefied for external market or for final waste disposal deep into underground of fuel sources/aquifers and where appropriate as a working fluid for feeding the fuel (30), and when appropriate stiH one more recycled part of said carbon dioxide is possible, representing an inner cycle, through fee addition of alkaline earth metal into the recycled condensate (32) in order to essentiaHy absorb said carbon dioxide from the gas phase, whereupon fee content of said carbon dioxide into said condensate is desorbed/released during fee reaction progress into fee reaction chamber (1), which said alkaline earth metal can after fee reaction progress be recovered as a phase of soluble soHd and or molten material (18) preferably utilized for another of said inner cycle.

10. Method according to any of preceding claims, c har a c t e r i z e d i n that when presence of alkaline and/or sulphur agents and/or compounds into the fuel, and or after addition to the fuel of said agents and/or compounds, the process criteria of fee reaction progress are preferably as partial oxidation of the fuel during high process pressure, preferably 30 - 220 bar (a), more preferably 50 - 150 bar (a), wife high steam partial pressure, preferably 20 - 150 bar (a), more preferably 35 - 110 bar (a), and from carbon conversion point of view lowest possible reaction temperature, preferably 820 -

fee reaction progress by recycling carbon dioxide C0₂, for spfit of alkaline compounds essentiaHy as a phase of sofid and/or molten material as weU as of sub-/microscopic and visual dust particles (comprising fumes) into fee gas phase, wife the sulphur compounds essentiaHy as a part of fee gas phase.

11. Method according to any of preceding claims, c h ara c t e r i z e d i n that when partial oxidation of a sulphur containing fuel (3 ) fee produced fuel g^s contains hydrogen sulphide H₂S, said hydrogen sulfide or apart thereof, is - selecfivelytecovered by at least one-preferably

Purisol-or-Arnin-process for a selective and regenerative absorption of the H₂S~content or by a corresponding method, wife a foHowing step of reversible thermal decomposition of hydrogen sulphide H₂S, preferably pressurized and preferably counter current to recovered sulphur melt S versus said flow of hydrogen sulphide, at a temperature over 300°C, to elementary sulphur S and/or poly-sulphide S_x ^2~and hydrogen H₂, alternatively by selective recovery of said hydrogen sulphide from the gas phase directly by converting, by at least one and preferably pressurized, recycling anthraquinone AQ-/ anthrahyαfoqulnone AHQ-mefeod ( 1-64) or other method with similar function, or in combination with fee above said methods for production of elementary sulphur S (69), hydrogen H₂ (68) and/or hydrogen peroxide H₂O₂ (37), with fee possible integration of at least one, preferably pressurized, fuel ceH (122) method for production of power (20) and steam (123), said steam feeding at least one steam turbine (124) with attached generator (125) for generation of power (20), wife said fuel cell fed by hydrogen (68) preferably produced wifein fee present method, whHe the rest part of produced chemicals are recycled wifein fee method and/or to be brought out from fee method fee fuel gas content of remaining hydrogen sulphide H₂S as weH as apart of carbon dioxide CO₂ are absorbed by a recycling alkaline solution (18 A 1 SB) loop foUowed by desorbing said gaseous chemicals into the reaction chamber (1).

12. Method acwrding to Claim 11 , c h ar a c t er i z e d i n that fee AQ-/AH -method (61-64) is integrated wife production of deHgπification Hquors within pulping processes by

(67) and/or apart of recycled AQ-flow (65) constitute additives to nearly sulphur free green Hquor or low sulphidity green Hquor (ISA) and elementary sulphur S (69) Is added to nearly sulphur free white Hquor or low sulphidity white Hquor (55) for production of poly-sulphide (58) as a

13. Method according to any of fee preceding claims, c h ara c t er i z e d i n feat when combustion during partial oxidation of residual Hquors/products from pulping processes by at feast two reaction chambers, said chambers are operating during quite different process criteria wife fee one reaction chamber (1A) mainly acting for spfit of alkaline and sulphur compounds, wMle fee other reaction chamber (IB) acting during quite different process criteria, essentially for direct conversion production of high sulphidity white liquor (18B) by adding recovered elementary sulphur S (69) to fee other reaction chamber (1-B) of- low-process -pressure, preferably -1,-10 - 4,00 bar (a); -more preferably 1,30 - 2,30 bar (a), of low steam partial pressure, preferably 0,20 - 0,95 bar (a), more preferably 0,30 - 0,55 bar (a), witrήn temperature interval of 900 - 1100°C, preferably 950 - 970°C, whereby the equfebriurn reaction during the reaction progress is displaced, which moves a bigger part of the sulphur content preferably 75 - 95 %, more preferably 85 - 90 %, out wife the phase of soHd and/or molten material (18B) from said other reaction chamber (IB) as alkaline sulphide Na₂S (18B) with fee remaining sulphur compound as a part of the gas phase as hydrogen sulphide H2S, which part of said remaining sulphur content previously and selectively is partially absorbed by aU fee flow or a part of fee black Hquor flow (30, 31) before feeding said black Hquor into said other reaction chamber (IB), whereupon the gas ^"phase (38B) comprising fee rest part of fee sulphur content H₂S Is pressurized by compressor (82), and brought together with from reaction chamber (1 A) leaving flow of fuel gas (38 A), preferably by an in-tapping of expansion turbine (2).

14. Method according to any of the preceding claims, c h ar a c t e r z i e d I n that fibre partial processes wifein a pulping manufacturing process is integrated wife recovering energy and chemicals essentiaHy by fee following process steps as a whole or parts thereof:

• Digester pressure unchanged or increased 1 bar, or more.

• Digester spent Hquor/black Hquor (30, 31) is fed during nearly preserved state of pressure and temperature to a preparatory process step for ordinary or preferably restricted increase of DS-content preferably u to fee level of DS-content where fee solubifity of sulphate soap and other included chemicals are preserved, which means a DS-content of interval 30 - 50 %, more preferably 35 - 45 % before feeding fee reaction chamber (1).

• Not condensable gases NCG (90) preferably integrated with evaporation plant by sys'te nxbr negative pressure/ ac^^

• Bleach plant effluent (87) feeding fee reaction progress for recovering energy and chemicals. • Chips pre-heating in at least one chip bin (97) by gas phase comprising fee rest content of heat moisture and chemicals, preferably within a later part of expansion cooHng sequence, more preferably by gas phase (45) after completed said expansion cooHng sequence. • Chips pre-treatinent in at least one pre-treatment vessel (98) by pressurized gas phase comprising aU the hydrogen sulphide H2S-cont nt or a part of said hydrogen sulphide,

-- preferably wife expansion-coohng sequence:- -- - - - • Pulp washing in at least one vessel (99% of aH kind of system comprising counter current, co current and radial water flows, ^"by segregated recovery of clean and tempered condensate (33), preferably comprising dissolved carbon dioxide CO₂. • Bleaching agents comprising nearly sulphide free alkaline NaOH from spfit of alkaline and sulphur compounds wi hin fee present method as weH as oxygen O₂, h drogen peroxide H₂O₂ and ozone O3 and when appropriate comprising feeding of said chemicals to reaction progress of reaction chamber as a whole or parts thereof. • Closed cycle for aU fee recovery plant chemicals, except separation of non process elements NPE, during high process pressure adjusted to the digester pressure, preferably except fee reaction chamber (1) process wife preferably a higher process pressure, comprising pressurized production of nearly sulphide free white Hquor or low sulphidity white Hquor (55) as well as high sulphidity white Hquor (55 A) and nearly sulphide free green liquor or low sulphidity green Hquor (18 A) wife addition of AQ (65) and nearly sulphide free white Hquor or low sulphide white Hquor wife addition of elementary sulphur S (69) according to claim 12, as a whole or parts thereof according to existing requirements.

15. Method according to any of fee preceding claims, c har c t e r i z e d i n feat when combustion of a fuel during partial oxidation for production of synthesis gas, with further processing to for example hydrogen peroxide H₂O₂, hydrogen H₂, ammonia NH₃ as a whole or parts thereof, and/or processing to methanol CH₃OH, synthetic diesel, dhnefeylether DME or other mobile fuels, and/or production of said synthesis gas for an Integrated Gasification Combined Cycle (ΪGCC), the expansion cooHng through at least one expansion turbine during at least one partial step is appHcable as a preparatory gas cleaning step during generation of power (20) or by said expansion turbine

1 . Method according to any of fee preceding claims, c h ar a ct eri z e d in that when combustion during partial and/or total oxidation of fee pulping process sulphite and/or sulphate spent Hquor/black liquor, mixed or separate, wife recovering chemicals in form of alkaline compounds as a phase of sofid and/or molten material (18) and or into gas phase containing sub-/microscopic (comprising fumes) and visual dust particles, wife sulphur compounds essentiaHy into fee gas phase as sulphur dioxide SQ₂ directly during total oxidation or when reaction progress takes place during partial oxidationrfee-hydrogen sulphideHbS is oxidized during the foUowing gas burning (-1C_; 12) to said sulphur dioxide, whereupon said sulphur dioxide is selectively absorbed by at least one solution (183) of said alkaHne compounds for direct conversion production of active digesting Hquors within sulphite based pulping processes.

17. Method according to Claim 16, c h ar a c t e r i z e d i n feat the recovery of alkaline compounds preferably constitute a sodium hydroxide NaOB-cΛntaϊnϊng carbonate Na Cθ₃-solution (18), alternatively a carbonate Na CC^-solution (18A), and/or a bicarbonate NaHCθ3-soIution (18BB), as a single mixed solution oτ as carbonate and bicarbonate solutions separately, according to predestinated process requirements, through avoiding or acting for carbonizing by the gas content of carbon dioxide CQ2, preferably during pressurized operation.

18. Method according to any of fee preceding claims, c h a r a c t e r i z e d i n that when need for an additional fuel and/or when insufficient amount of recovered chemicals, or when recovering Is not possible, for the reaction progress into fee reaction chamber and/or for the mill chemical balance, additional suitable make-up chemicals are added as for example magnesium sulphate, magnetite, ammonia, calcium oxide, calcium sulphate, sulphur (69), petroleum coke (103), black Hquor (30), sulphate soap (102), sodium sulphate and/or sulphate ash (101) according to existing process requirements, when dry suppfied parts preferably takes place pneumatfcaHy direct into fee reaction progress, by for said reaction progress appropriate gas, preferably by oxygen containing gas as an agent of conveyance.

19. Method according to any of preceding claims, ch ara ct eri z e d i n feat when combustion of a fuel containing chlorides, said chlorides are during the reaction progress converted to hydrogen chloride constituting a part of fee gas flow and said hydrogen chlorides are removed as chlorhydric acid by at least one washing step into a scrubber or correspondingly, preferably by cold water, more preferably recovered cooled condensate from fee last expansion turbine cooling stage, by a gas wash preferably through at least one Hquid ring pump (9) or ofeer devise wife corresponding function.

20. Method according to any of fee preceding claims, c h ar a c te ri z e d i n that when combustion of a fuel by partial oxidation during a first pressurized reaction progress into at least one reaction chamber, fee fuel gas (38) part of chemical energy is utilized for recovering energy and when appropriate also chemicals, when said energy recovery takes place by at least one second combustion, pressurized or atmospheric unit during total oxidation into said second reaction chamber (IC) or gas boiler (12), or ofeer devise wife corresponding function, preferably wife additional fuel supply (30C, 21) to said secondary combustion, wife fee purpose of reheating fee flow of gas and/or condensate within the method and preheating the fuel and/or oxidation agent and/or ordinary steam production for mUl internal use, preferably high pressure steam (89) feeding at least one steam turbine (120) with power generator (121) for power generation 20, said steam turbine is preferably integrated into fee expansion cooHng method, said energy recovery as a whole or parts thereof.

21. Method according to any of fee preceding claims, c harac t e ri z e d in feat when at least two stage combustion of a first fuel (30, 30A, 30B) by at least one first reaction chamber (1) during partial oxidation followed by at least one second reaction chamber (IC) during total oxidation, when gas phase after partial o idation (38) is totafiy burned out into said second reaction chamber, with or without any additional supply of a second fuel (30C) diiring total oxidation, while produced gases (38, 38C) of respective reaction chambers (1 , IC) are both said gases cooled by at least one expander turbine step of at least one partial step wife completed expansion of integrated gas phases into at least one common expander turbine step of at least one partial step to for following recovery appropriate counter pressure, preferably down to negative

are recovered out of reduced gas phase (40/400) as a product 401, and or OUL of oxidizing gas phase (40C/4Q0C) as a product 401 C, and/or as a phase of soHd and/or molten material (18, 18A, 18C), and/or as dust particles and heavy metals into condensate (32, 32C), wife or wifeout addition of heavy metal b ding agents (300) into said condensate, as a whole or parts thereof.

22. Arrangement for recovering energy and when appropriate also chemicals, fee recovery of said chemicals comprising a part or parts ofi phase of sofid and/or molten material, sub-/rmcτoscopϊc (comprising fumes) -and or visual dust particles; gas components and as water solutions, from a fuel comprising a part or parts of: hydrogen, hydrocarbon and hydrogen compounds, which arrangement comprising at least one reaction chamber (1) during at least one reaction progress for combustion/thermal decomposition during partial and/or total oxidation by reaction progress wifein a pressure interval of 2 - 220 bar (a) and a temperature interval of 600 - 3100^QC, and a device for cooHng produced gas containing chemical and/or physical energy by condensation of into said gas vaporized agents and/or compounds, c h arac t e ri z e d i n that fee arrangement comprises:

• one or more reaction chambers (1 ) for realization of the reaction progress.

• said reaction chambers are acting during different process pressures and/or different stoichiometri, which at least one of said reaction chambers at reducing progress (1) and at least one of said chambers at oxidizing progress (1 C), when preferably fee reaction chambers are arranged in series.

• one or more pressurized slag separator/dissolver/quench of phase of sofid and/or molten material (18, 126) arranged after fee reaction chamber when water or water containing agents Is added to said device for dissolving said phase of solid and/or molten material before and or after gas separation, when necessary avoiding carbonation.

« said cooHng arrangement comprising one or more expansion turbines (2, 4, 6), when each step comprising one or more partial steps, for gas cooling by condensation of vaporized agents and or compounds.

• said cooHng arrangement comprising one or more turbine steps of expansion cooHng and/or partial steps, which can preferably be arranged as one single unit/multistage expander turbine.

• said cooling arrangement comprising device for elimination of gas content of sub-/mιcroscopic comprising rumes) arid visual dust^'particles^{^}wneh saiddustp irficles constitutes condensation nuclei for vaporized, condensable agents and/or compounds, whereupon fee weight of said dust particles is increased, said dust particles are falling out of the gas phase with transfer of said dust particles into fee condensate phase. • at least one expansion turbine driven generator (3, 5, 7) for power (20) production. • at least one expansion turbine for driving a stationary apparatus, via mechanical and or hydraulic transmission or correspondingly, as compressor for combustion air (8) and compressor for gas (82) and any kind of heat pump or correspondingly or expansion turbine drive of mobfie raachine/apparatus (83 A) constituting any kind of means of transport as vehicle on ground, atinto sea and into air. • said expansion turbine constructed in materials resistant to erosion and or corrosion at exposed parts, and preferably adapted for relative high steam partial pressure, when and where needed • at least one separation device (14, 15, 16) for separation of gas phase and condensate phase after expansion turbine steps and or partial steps. • at least one device, preferably pressurized, for recovering chemicals by conversion/thermal decomposition of hydrogen sulphide H₂S, said device preferably comprising pressurized fuel ceH (122), of which supply of hydrogen H₂ preferably is produced within said device for recovering said chemicals and for generation of power (20) and high pressure steam (89).

• at least one steam turbine (120) wife at least one generator (121 ) for production of power (20) wife for said steam turbine and expansion cooling turbine coordinated arrangement for condensate handling.

• one piping-, fan- and pump-airangement with control- and regulating device for fee flows of gas, steam, condensate, fuel atomization- and oxidizing agents, comprising possibilities of integration with ofeer arrangements for exchange of media, comprising condensate (120, 151, 321) and not condensable gases NCG (90).

» at least one compressor (8) for feeding compressed air (35) into reaction chamber

(1).

• one negative pressure/vacuum strengthening arrangement, when needed a pluraHty of steps, as vacuum pump (10), steam ejector, any kind of Hquid ring pump (9) or corresponding device as turbo fan, jet of Hquid pump, barometric condensate fall leg wife water-seal and g /tufbo fan (11) as a whole or parts thereof, comprising possibilities of integration wife other needs of arrangement of negative pressure/vacuum as fee non condensabie as NCG 9ό)-syst^'eni of fee evaporatibn^~p an ^"' at least one storage tank (1 ) for expansion cooled condensate (34) preferably from the condensate separation device of fee last step and/or partial step of fee turbine expansion cooHng. • at least one reaction chamber (IC) or gas boiler (12) for total oxidation/combustion of fuel gas from precedfegf eaction chamber (1) during partial oxidation, whereupon said gas bofier preferably is equipped with heat exchanging elements for pre heating suitable media and/or for ordinary steam production- • at least one condensation device (22) for cooling fee flue gas (45), said device ^~co rising refi^ear g^ ^uItable media,- said device-also comprising possibiHty for recovering fee carbon dioxide CQ2 content as being fee essential part of said flue gas, said carbon dioxide to be discharged as a stack gas and/or partly returned to fee reaction chamber and/or to be brought out and used wifein ofeer markets after liquefying and/or final waste disposal, as a whole or parts thereof

23. Arrangement according to Claim 22, c h ara c t e r i z e d in that the reaction chamber (1) of fee reaction progress consists of any kind of known engineering and apparatus technology comprising principles as: combustion chamber, up flow, molten bed, bubbling fluidized bed, fluidized bed and entrained flow, preferably comprising at least one ceramic- and or cooling tube in-lined reaction chamber, corresponding wi h said principles of apparatus technology analogous arrangements for separation and handling/treatment of produced phase of sofid and or molten material after fee reaction progress wife moistening fee gas phase before and/or after said separation of said phase of sofid and/or molten materiaL

24. Arrangement according to any of Claim 22 or 23, c har ac t e r i z e d i n that a fuel burner nozzle of fee reaction chamber burner arrangement consists of any kind of known engfeeering and apparatus technology comprising principles as multi hole nozzle, single hole nozzle, vortex nozzle, venturi nozzle, infra sound nozzle and ultrasound nozzle, either as one single nozzle or as a plurafity of nozzles, wife steam and or any kind of gas as atomization- and forcing agents for wet fed fuels and pneumatic fluidized conveyer system when dry fed agents or compounds comprising bio fuels, carbon powder, petroleum coke, sulphur, calcium sulphate, sodium sulphate and sulphate ash, according to existing requirements, wife both fee feeding systems at the same

^'i me^'Or ohry one^' oi said^" s tems-^"

25. Arrangement according to any of fee Claims 22 - 24, char a c t er i z e d i n feat It includes at least one static and or dynamic contact device for selective recovery/absorption of recoverable gas part of the gas phase, which said dynamic contact device Is preferably of type rotating device wife extremely short time of contact between said gas phase and absorbing Hquid, more preferably a rotating device of type liquid ring pump (9), most preferably Hquid ring pumps in series to the gas flow counter current fed cooling and sealing liquid constitutes, when appropriate, absorption agent for selective ~absoτption-of said recoverable gas part preferably by alkaHne solution for said selective absorption of said recoverable gas part wife preferably said cooHng and sealing liquid of the last step of said type of Hquid ring pump to be cold water for gas washing.

26. Arrangement according to any of the Claims 22 - 25, c h ara c t eri z e d in that after fee reaction progress a number of process steps are coordinated in at least one multi functional apparatus (126A, 126B). preferably pressurized, according to fee site into fee arrangement representing a device for dissolving a phase of solid and/or molten material and/or for sepajafing gas and Hquid phase, furfeer slaking chemicals/substances in oxide form for transmission into hydroxide form, and arrangement for avoiding or acting for carbonizing the chemicals and to be a receiver of additional chemicals, as a whole or parts thereof according to process requirements, said process steps - when needed - during effectual contact during intensive stirring between the phases of gas (40) and Hquid (127) through inside fee said multi functional apparatus placed concentricaHy formed intermediate walls (125) creating a form of multi stage Hquid-lock, the bottom part of said intermediate walls preferably designed wife a saw-toothed performance (125B) for fee very best flow distribution said waH turns around