METHOD OF TREATMENT OF SYNTHESIS OF - GAS AND SYSTEM, USING COPPER CATALYST IN TWO-STEP REACTIONS AT 475 - 525 °C AND 250 - 290 °C

Method of treatment of synthetic gas and system, using copper catalyst in two-step reactions

At 475-525 and 250-290 ° with

True form-to thermal conversion of organic substance, for example, wastes on organic basis, biomass and T. d ., synthesis-gas. In particular, it relates to conditioning synthesis of-gas for change of content in it ng and with.

On synthesis-gas mainly influence: characteristics of the composition of the initial thermally transformed substance (elementary composition, energy value, moisture content, physical properties), conditions of gasification (oxidizers, temperature, pressure, residence time), and also type of used gasifiers (with stationary layer, with fluidized layer, with gasification in flow, reactor periodic action). However, as only above mentioned factors are determined, synthesis-gas, in particular ng, with, an, and ratio ng/with will is thermodynamic a balance within limits of certain range.

Synthesis-gas frequently not will correspond to specific requirements to gas in the fields of industrial application, for example, synthesis of-gas for engines, effective for converting synthesis of-gas into electric energy, will require certain composition synthesis of-gas for effective and efficient operation. Accurate requirements will depend on production process, but frequently differ from natural composition of produced gas.

Respectively there is need in further controlling or change of composition of synthetic-gas for compliance with specific requirements (concentration of ng, rationg/with) areas of industrial application. This may be achieved by changing the parameters of the method of production of synthesis-gas, but such decision require, to synthesis of-gas should be regulated rather composition gas, and not efficiency system, and this per se means Your lu efficiency of processing organic substance, that undesirable.

The present invention reduces, at least, partially indicated above problem with known systems.

In accordance with the first aspect of the present invention proposes a method diffusion condensate ratio with to ng synthesis-gas, including: passing synthesis of-gas through first reactor, containing xi, at the first temperature, effective for interaction of CO2 synthesis-gas with xi with formation of copper oxide and with; lower lu temperature of synthetic gas to the second temperature, effective for interaction of hydrogen in synthesis of-gas with copper oxide with formation of xi and Η2Ο , and; passing synthesis of-gas through the second reactor, containing copper oxide, so that Η2 synthesis-gas interacts with copper oxide.

Preferably method additionally includes passing synthesis of-gas through the first heat exchanger to passing through the first reactor, with the aim of Your condensate temperature synthesis of-gas to the first temperature. The first temperature may be in range from 475° with to 525° with, preferably first temperature is 500° with ± 5° with.

Preferably lower lu temperature of synthetic gas to the second temperature includes passing synthesis of-gas through the second heat exchanger. The second temperature may be in range from 250° to 290° with, preferably the second temperature is 270° with ± 5° with.

Method can additionally include passing synthesis of-gas, coming from the second reactor, through the third heat exchanger, for diffusion condensate temperature synthesis of-gas to the first temperature, and recirculation synthesis of-gas through first and second reactor for reaching any from required values: content Η2, content with or ratio with to Η2; and, as only content of ng, content with or ratio with to Η2 achieved, -removal of synthesis of-gas. Synthesis-gas downstream from the second reactor can be checked and recirculation synthesis of-gas can be adjusted for maintaining any of required values: content Η2, content with, or ratio with to ng ·

Preferred version of the method may additionally include reversal of flow of synthesis of-gas through system of so, that synthesis of-gas at the first temperature is directed into the second reactor, temperature synthesis of-gas then is reduced, and synthesis of-gas with lower nnoi temperature then is fed into the first reactor. Check gas flow at the first temperature through the second reactor causes interaction SΟ2 synthesis-gas with xi with formation of copper oxide and with, thereby but copper oxide in the second reactor, and check flow of gas at second temperature through first reactor causes interaction of ng synthesis-gas with copper oxide with formation of xi and Η2Ο , thereby but copper in the first reactor.

Change of composition of synthesis of-gas with passage of time can be checked for determining reaction ability of substance in reactors, and if reaction ability becomes lower required reaction capability, direction of flow through reactors may be reversirovano.

Method can include: check of composition synthesis of-gas, to determine, comes off whether speed of oxidation reaction of copper from the speed of the reaction of reduction of copper oxide, and if the rate of oxidation reaction of copper actually lags behind the rate of reaction of copper oxide, -reduced heat of, removed second heat exchanger, for diffusion condensate the second temperature. Preferably, check of composition synthesis of-gas for determining, comes off whether speed of oxidation reaction of copper from the speed of the reaction of reduction of copper oxide, includes determination of combination of tendency to Your Exploration content with at least with one of such values, as low content of ng and diffusion nnoe content NgO.

Method can include: check of composition synthesis of-gas, to determine, comes off whether of reaction rate of reduction of oxide copper from oxidation reaction rate of copper, and if the rate of reaction of reduction of copper oxide actually lags behind rate of oxidation reaction of copper, -reduced heat of, removed second heat exchanger, for lower condensate the second temperature. Preferably check of composition synthesis of-gas, to determine comes off whether speed of oxidation reaction of copper from the speed of the reaction of reduction of copper oxide, includes determination of combination of high content of with at least with one of the tendencies: diffusion condensate content Η2 and lower condensate content Η2Ο.

Method can include purification cycle, which includes: disconnecting of reactors and the first heat exchanger from flow of synthesis of-gas; and passing the gaseous nitrogen with temperature above 650° with through reactors for removing from them carbon deposits. Substance in reactors can be subjected to vibration, to enable removal of from it carbon deposits.

Preferably method includes pyrolysis or gasification of organic substance for production of hot synthesis of-gas, containing more than 30% with, above 20% Η2, and also SΟ2 and Η2Ο for use in the method.

According to the second aspect of the invention, device is offered for realization of the method of the first aspect of the invention, containing: first heat exchanger, having inlet and outlet for hot synthesis of-gas; first reactor, containing xi, having inlet for receiving gas from the first heat exchanger, and output;

second heat exchanger for receiving synthesis of-gas from the outlet of the first reactor; the second reactor, containing copper oxide and having inlet for receiving synthesis of-gas from heat exchanger, and output; and control agent, made with the possibility of control of the first heat exchanger to lower condensate temperature passing through it synthesis of-gas to the first temperature, effective for interaction SΟ2 synthesis-gas with xi in the first reactor with formation of copper oxide and with, and to control second heat exchanger to lower condensate temperature passing through it synthetic gas to the second temperature, effective for interaction Η2 synthesis-gas with copper oxide with formation of xi and Η2Ο.

Preferably control agent functions with the aim of controlling the first heat exchanger for lower condensate temperature synthesis of-gas to range from 475° with to 525° with, more preferably 500° with ± 5° with.

Preferably control agent functions with the aim of controlling second heat exchanger for lower condensate temperature synthesis of-gas to range from 250° to 290° with, more preferably 270° with ± 5° with.

Device can additionally contain: line recirculation of flow synthesis of-gas from output from the second reactor to input to first reactor for recirculation of synthesis of-gas through reactors, and third heat exchanger, located in recirculation line synthesis of-gas; sensor for determination of one or several of the following indices:

content of ng, contentwith, ratiowith tong, and content ofΗ 2Ο synthesis-gas; where control agent is made with possibility of regulating gas recirculation via line recirculation of flow synthesis of-gas in accordance with measured one or more values: content of ng, contentwith, ratiowith tong, for achieving one or more of required values: content of ng, contentwith, ratiowith tong; device additionally contains output conditioned synthesis of-gas, designed for abduction synthesis of-gas.

Device can additionally contain valve device, driven by, to reverse flow of synthesis of-gas through first and second reactor and second heat exchanger so, to synthesis of-gas at the first temperature passes through the second reactor, and synthesis of-gas at second temperature passes through first reactor.

Preferably control agent is made with possibility to control change of composition of synthesis of-gas with passage of time for determining reaction ability of substance in reactors, and if reaction ability drops below required reaction capability, to activate valve device, to reverse direction of flow through reactors.

Preferably control agent also is made with possibility to control synthesis-gas with passage of time, to determine comes off whether speed of oxidation reaction of copper from the speed of the reaction of reduction of copper oxide, by determining combination of tendency to lower Exploration content with at least with one of indices: low content of ng and diffusion nnym content of NgO ; and if the rate of oxidation reaction of copper actually lags behind the rate of reaction of copper oxide, -to regulate second heat exchanger with the aim of diffusion condensate the second temperature.

Device may contain bypass pipe of third heat exchanger, at control agent additionally is made with possibility to control synthesis-gas with passage of time, to determine, comes off whether of reaction rate of reduction of oxide copper from oxidation reaction rate of copper, by determining high content of with in combination at least with one of the tendencies: diffusion condensate content of ng and lower condensate content NgO ; and if the rate of reaction of reduction of copper oxide actually lags behind rate of oxidation reaction of copper, bypass third heat exchanger with the aim of lower condensate the first temperature.

In one preferable variant of device additionally contains: valve device, designed for disconnection of reactors and the first heat exchanger from flow of synthesis of-gas; supply pipeline N2; valve device, designed for passing gaseous nitrogen at temperature above 650° with through reactors for removing from them carbon deposits. Preferably device additionally contains vibrator for vibration substance inside reactors, to enable removal of from them carbon deposits.

In preferable version of device also contains plant pyrolysis of organic substance for production of hot synthesis of-gas, containing more than 30% with, above 20% Η2, and also an and NgO.

Embodiment of the Invention described below with the help of example, with a reference to the drawings, on which:

on Figure 1 is indicated principal diagram of the device of the invention in the first mode of operation;

on Figure 2 is indicated principal diagram of device-in the second mode of regeneration of reactors;

on Figure 3 is indicated principal diagram of the device of the invention in the third mode of operation of; and

on Figure 4 is principal diagram of the device of the invention in the fourth mode of operation of, of removing carbon from the system.

Turn now to Review Figure 1, on which is indicated principal diagram of the device of the invention. Device has first reactor 10 and the second reactor 12, communicating fluid medium with each other through pipeline 14. Between reactors 10 and 12 is located heat exchanger 16.

Device also contains heat exchanger 18, having input 20 for reception of the hot synthesis of-gas and exhaust pipeline 22 for delivery of synthesis of-gas from heat exchanger 18 into reactor 10. Pipeline 24, having built fan circulation of 26 and passing through heat exchanger 28, forms line recirculation of flow between reactors 10 and 12.

Reactors 10 and 12 contain mixture, containing copper and copper oxide. One of the reactors 10 will contain greater than copper, and the other reactor 12 will contain greater than copper oxide at initial stage of the method.

Hot synthesis of-gas at temperature of approximately 900° with, enriched with (more than 30%)and Η_{2 (} more than 20%), with remaining part, consisting of S0_2, Η_{2 0} and hydrocarbon gases together with other secondary gas components, enters first heat exchanger 18, which may be heat exchanger of any known type, suitable for using with hot gas composition. Since hot synthesis of-gas passes through heat exchanger 18, it gives part of its heat, so that temperature synthesis of-gas at the outlet from heat exchanger 18 along pipeline 22 is approximately 500° with. Gas at 500° with has pressure approximately in one atmosphere and passes through reactor 10 so, that it has residence time in reactor less than two seconds. These conditions is shifted reaction, flowing in reactor 10, in direction of oxidation of copper, at that reaction next:

Xi + S0_2- ► SiO + with (reaction 1).

Respectively, in the first reactor 10 oxidation takes place of copper in copper oxide and, in that the process of oxygen is released from carbon dioxide, with its transformation to carbon monoxide, which is fuel gas.

Synthesis of-gas, containing less than S0_{2 and more} with, comes out from reactor 10 along pipeline 14 and passes through heat exchanger 16. Heat exchanger 16 withdraws heat from passing through it synthesis of-gas so, that temperature outgoing flow synthesis of-gas from heat exchanger 16 is approximately 270° with. This synthesis of-gas with lower nnoi temperature passes through reactor 12 at pressure of approximately one atmosphere and has time in stay it less than two seconds. These conditions is shifted reaction, flowing in reactor 12, in direction of reduction of copper oxide, at that reaction next:

SiO + Η_2- " xi + Η_{2 0} (reaction 2)

At this lower temperature hydrogen in gas flow reacts with copper oxide in a reactor with formation of a copper and steam.

Reaction, performed in reactors 10, 12 are reversible okislitelnovosstanovitelnymi (redox-) reactions, in which passing through reactors gas will react on one of said above reactions. Reaction, leaky inside reactor, will be determined temperature and other conditions gas passing through it. In reactor, receiving synthesis of-gas at higher temperature, conditions is displaced oxidation-reducing reaction in significant degree to oxidation, and in the other reactor, when temperature synthesis of-gas in it is approximately 270° with, conditions is displaced oxidation-reducing reaction in significant degree in direction of restoring.

These two reaction, taking place in reactors, is brought to increase of content of carbon monoxide in passing through them gas and to reduction of hydrogen content in synthetic gas. Purpose of the of this method consists in adjusting content Η2 and, more specifically, in the continuous its reduced with controlled rate, at simultaneous formation of additional with, thereby move common synthesis-gas to the more low relative ng/with without reduce heat of fuel combustion due to a simple depletion of Η2, since method leads to concentration with synthesis-gas reaction 1. United reaction 1 and the reaction 2 will act similarly reverse reaction water gas conversion, as shown below:

Η_{2 +}S0_2- > S0 + Η_{2 0}

Xi and SiO can be considered as broadening as catalysts in above given total reaction. Two-stage method is intended for achieving more high efficiency of Your condensate content Η2 by means of selection of various temperatures of the reactor and preferable catalytic compositions. Besides, this two-stage method allows better regulate performed reaction and direct equilibrium reaction in side from forming liquid products, such as methanol and other light hydrocarbons.

System is provided with pipeline 24 for recirculation, which leads from outlet from reactor 12 to input of reactor 10. This pipeline passes through the third heat exchanger 28, which raises temperature of gases back approximately to 500° with. Heat exchangers 18 and 28 can be part of one and the same heat exchanger, at that, heat, removed from coming into heat exchanger 18 gases, is used for diffusion condensate temperature synthesis of-gas in heat exchanger 28, thereby preventing the necessity of delivering additional heat into system for diffusion condensate temperature of recirculation gas back to required temperature approximately recirculating fan 26 is provided in pipeline 24 for recirculation of gas through reactors 10, 12 and heat exchanger 16. Sensor gas 30 controls quality of gas, circulating in system, for example, by determination of content of one or several of the following components: hydrogen, carbon monoxide, carbon dioxide, ratio of hydrogen to carbon monoxide, or steam. Recirculating fan 26 is controlled by the control apparatus (32, Figure 3) depending on the detected quality of gas. In process of operation control agent controls fan 26 for recirculation of alternating amount of gas, passing inside system, that can be achieve required quality synthesis of-gas.

With passage of time copper inside reactor 10 will oxidize with formation of copper oxide, and copper oxide inside reactor 12 achievable to copper, which will lead with passage of time to reduction of efficiency of the system. Sensor 30 reveals this by means of permanent quality control of gas. For example, this can be realized with the aid of of checking content of carbon monoxide and hydrogen with passage of time together with number of recirculating gas, and, if all larger and greater amount of gas to be direct to recirculation for obtaining required co and ng, or if, despite recirculation gas, hydrogen content and carbon monoxide gradually is started be returned to communication means in inlet synthetic gas, then can be come to lead, that reaction slowed or ceased:

Reaction 1:xi + an ->SiO + with... retardation/termination reaction

Reaction 2 : SiO + ng >-xi + NgO ... retardation/termination reaction

and that larger part of substance in reactors reacted, or at least sufficient amount of substance in reactors 10, 12 acted, so that reaction rate of residual substance in them is not creates desired effect, then, as shown on Figure 2, valves 32 and 34 can be used for reversing direction of flow synthesis of-gas through reactors 10 and 12 for recovery of copper and copper oxide in reactors.

This reverse regeneration of converts copper, accumulated in reactor 12, in copper oxide, and copper oxide, pent up in reactor 10, in copper. This is realised with the help of reversing flow of synthesis of-gas so, gas, passing through reactor 12, has temperature, at which in reactor prevails reaction oxidation of, and that in other reactor 10, receiving synthesis of-gas with more low temperature after passing through heat exchanger 16, prevails reduction reaction. Such by both of reactor 10, 12 regenerated.

Since system continues to control quality of gas, direction of flow through system can be changed by direct to opposite, order to permanently expend and regeneration of copper and copper oxide in two reactors 10, 12.

Recirculating fan 26 operates in reverse direction, so that some amount of synthesis of-gas recirculates through reactors in direction, opposite shown on Figure 1.

Possibly, in the course of realization of the method, reaction in one of the reactors 10, 12 can be separated from reaction in other reactor, for example, if the reaction of oxidation of lags behind reduction reaction, then will is seen, that content of carbon monoxide in gas is not, or not increased in the same degree of, and content of hydrogen in gas decreases in the first scenario as follows:

Reaction 1:xi + SΟ2 -> SiO + with... decelerated

Reaction 2 : SiO + ng >-xi + Η2Ο ... flows along-still

At the other side, if reduction reaction lags behind oxidation reaction, then will is seen, that content of hydrogen in gas is not is reduced or does not decreases in the same degree of, whereas the content of carbon monoxide in gas continues to rise along the second scenario as follows:

Reaction 1:xi + SΟ2 -" SiO + with... flows along-still

Reaction 2 : CuO + Η2 >-xi + Η2Ο ... decelerated

As shown on Figure 3, if reaction oxidation of (reaction 1) lags behind reduction reaction (reaction 2), in accordance with the first scenario, the control system, containing control agent 32, reduces amount of heat, discharged from synthesis-gas in second heat exchanger 16, so, as the temperature of outgoing gas is from 270° with up to 500° with. Should have due to, control system, shown on Figure 3, is present invention, but not is indicated on other depicted for be. Control agent receives signals from inbuilt of sensor 30 and sends signals to different valves and heat exchangers of the device. Since hot gas, coming into reactor 12, later is at temperature of this area, above 270° with, used for displacement reaction in considerable degree to reduction reaction, diffusion lu temperature of this gas shifts the reaction from reduction reaction to oxidation reaction, and thus complements the action of reactor 10. In this mode of operation of gas in the range of temperatures from 210° with up to 500° with, passing through reactor 12, will to participate as in oxidation reaction, and in reduction reaction, originating in reactor. This allows oxidation reaction effectively ago reduction reaction since conditions is shifted reaction in both reactors more in the direction to oxidation.

If, at the other side, reduction reaction (reaction 2) lags behind oxidation reaction (reaction 1), as shown in the second scenario, then bypass valve 34 opens, at least partially, so that not entire gas, recirculating in pipeline 24 for recirculation, passes through heat exchanger 28. Such by mixture of incoming gas and recirculation gas, fed into reactor 10 has temperature below 500° with, in particular from 270° with up to 500° with. Since temperature synthesis of-gas, incoming in reactor 10, decreases, direction of oxidation-reducing reaction in it is displaced from oxidation of to restoration, at and oxidation and reduction will be to flow inside the reactor 10. In this mode of operation of larger amount of substance is accessible for reaction of reduction and smaller amount of substance is accessible for oxidation reaction, that allows reduction reaction discontinuities oxidation reaction.

Degree, to which one reaction lags behind the other, can be determined by measuring quality of gas, circulating in system. If one of the reactions begins to slow, then the other reaction at still flows, then can be it possible to consider, that one of the reactions lags behind the other, and control agent receives corresponding standard.

Should have in form, that this regulation may be performed independently from direction of flow through reactors 10, 12.

In pyrolysis reaction at is formed at least some amount of carbon black, which will be captured passing gas and, respectively, gas, coming in reactors 10, 12. This soot enters the reactors and forms deposit on surface of substance inside reactors, thereby reducing over time efficiency system.

As shown on Figure 4, if transducer 30 show total Your lu efficiency system of, for example, smaller conversion of ng at, independently from reversing flow through reactors, system can be removed from operation by stopping of supply to it synthesis of-gas. Pipeline 40 nitrogen feed 40 feeds hot gaseous nitrogen in system and directs it on circulation in it. Simultaneously heat exchangers 16, 28 are transferred into autonomous mode, and flowing through them gas due to this has diffusion nnuyu temperature, preferably approximately 600° with. The, as nitrogen passes through reactors 10, 12, it causes entrainment or gasification of any of carbon substances, which is coated with system from inside. To enable effective separation of carbon deposit from in reactor 10, 12, the bottom of the reactor can be subjected to vibration, to to cause vibration of copper and/or copper oxide inside. At other pipelines shown as autonomous, should have due to, that nitrogen can circulate through other pipe lines, to enable cleaning.

Be, as described above, to reduce the hydrogen content in synthetic gas and to enrich its carbon monoxide due to dissociation of carbon dioxide and copper regulated, at which the reduction reaction and the reaction of oxidation of oxidation-reducing reaction are simultaneously and successively one after another in separate reactors. This provides the greater regulation of oxidation-reducing reaction, allowing to selecting individual favorable temperatures of reaction in each reactor.

Due to regulation of temperatures and pressure of reactor declared here two-stage oxidation-reduction reaction of copper completely adjusted for displacement reaction in two reactors, that simulates reversible reaction water gas conversion. The fact of not less than, described in this document two-stage process promotes reversible reaction water gas conversion without operation at high temperature or diffusion nnom pressure, and all same provides more high conversion of carbon dioxide to carbon monoxide and more high efficiency Your condensate content Η2.

Due to separation of two stages described reaction and changing temperatures of gas, which passes through two reactor, where these two reaction are, system simply exploited for obtaining required ratio of hydrogen to carbon monoxide in the synthesis-gas.

Besides, due to separation of reactors so, that one half of oxidation-reducing reaction occurs in each reactor, and due to reversing flow in two reactors, catalytic material in both these reactors is subjected to regenerirovaniyu. As described above, this can take place automatically, without need of converting reactors in autonomous mode or replacement of their separate reactions of regeneration, T. e. substance in reactors constantly is consumed and regenerated with change direction of flow. Device and method allow chemical energy of hydrogen be transformed into chemical energy carbon monoxide such by, which does not alter negatively on efficiency of method of gasification or pyrolysis.