Method and apparatus for producing natural gas substitute

FIELD: chemistry.

SUBSTANCE: natural gas substitute is obtained from fresh crude synthesis gas 11 in a methanation section 10, having at least a first adiabatic reactor 101 and at least an additional adiabatic reactor 102-104, connected in series. A gas stream collected from the previous reactor of the methanation section is fed into each additional reactor 102-104, and at least a portion 22 of the reaction gas is recycled as input gas into at least one of said reactors. Fresh crude synthesis gas 11 is concurrently fed into reactors 101-104 and gas recycling is carried out by collecting a portion 22 of the reaction gas stream 20 from the first reactor 101 and the portion 22 of the gas is used as recycling gas to dilute the stream 12 of the fresh gas fed into the first reactor 101, to obtain a stream 18 of diluted gas at the input of the first reactor.

EFFECT: invention increases efficiency by reducing recycled gas consumption.

12 cl

 

The technical field

The present invention relates to a method for production of substitute natural gas (CYP or English. SNG). In particular, the invention relates to a method of manufacturing CYP by reaction of a synthesis gas containing hydrogen and oxides of carbon section mahanirvana consisting of adiabatic reactors with intermediate gas recovery. The invention relates also to a device realizing this method.

The level of technology

There is a continuous increase interest in technical production CYP. CYP is a clean fuel that can be distributed through existing pipelines and devices and be used as a substitute for natural gas in a wide range of applications.

A method of producing CYP includes mahanirvana synthesis gas (conditioned synthesis gas consisting of hydrogen and oxides of carbon. Using reaction mahanirvana conditioned synthesis gas turns into a more valuable product, containing not less than 95% methane (CH4) with small amounts of carbon dioxide, hydrogen and inert impurities, the Synthesis gas can be obtained by gasification of coal or biomass with additional advantages: RPG, a product of coal gasification has the advantage of being defined by the presence of extensive coal resources, CYP, the product of gasification of biomass does not increase emissions of CO 2on a global scale unlike other fossil fuels.

Basically, the way mahanirvana synthesis gas includes the following vysokoekonomichnyj reaction:

(I)CO+3H2CH4+H2O

(II) CO2+4H2CH4+2H2O,

in which reaction (1) has a thermal effect (enthalpy of reaction) to about 206 kJ/mol, reaction (2) about 165 kJ/mol.

In accordance with the prior art, the above reaction is carried out in the so-called section mahanirvana, consisting of a series of adiabatic reactors with heat recovery and recirculation of gas.

Reactors connected in series, that is, the fresh gas is fed into the first reactor and each subsequent reactor is fed partially converted gas stream is taken from the previous (upstream) of the reactor section. The reactor contains an appropriate catalyst, increased the non yield of the reaction.

To control for carrying out exothermic reactions and prevent excessive temperatures inside the reactors, which can damage the reactor and/or catalyst, use heat recovery and recirculation of gas. In particular, the heat recovery is carried out by means of heat exchangers, cooling the hot gas stream at the outlet of each reactor production of high pressure steam. Recycling is an additional measure of control of the reaction rate and the temperature inside the reactor by dilution of fresh synthesis gas fed to the first reactor, a part of the reaction gas. Recirculation gas requires the use of the corresponding compressor.

For example, a widely known method TREMP™ includes a section mahanirvana consisting of a first reactor which is supplied with fresh synthesis gas with an appropriate ratio of hydrogen/carbon, and two additional reactors. The reaction gas at the outlet of the first reactor passes through the superheater and boiler high pressure and is divided into two streams. One stream is directed to the second reactor, the other input of the first reactor through the gas heater and the compressor. In another known method, the flow of recirculating gas is selected after the second or subsequent reactor and is mixed with fresh gas supplied to pelvirectal, that is, the recirculation circuit includes all reactors section mahanirvana with the possible exception of the last reactor of the final product.

A common feature of known methods is full of fresh gas in the first reactor. Because proper thermal effect of reaction required high dilution, which causes the need for recirculation of the relevant part of the reaction gas. The ratio between the total molar flow rate entering the first reactor, and the molar consumption of fresh raw synthesis gas may reach the value of 6 or 7, this means that approximately 15-20% or even less gas in the first reactor is a fresh synthesis gas, while 80% or more recycled reaction gas.

Due to the above, the absorption of compressor energy for recirculation gas is quite high and thus the compressor itself is a large and expensive equipment. Another disadvantage is that the amount of recycle gas increases the gas flow in the reactor, mainly in the first, which requires the use of larger and more expensive units and larger amounts of catalyst.

All these deficiencies have a negative impact on the cost section mahanirvana and competitive price CYP in comparison with the price of operations the CSOs natural gas, on the other hand, the aforementioned high value of the coefficient of recirculation, in prior art, apparently, it is necessary to avoid overheating reactors.

The invention

The present invention is the creation of a more profitable and competitive way for the conversion of synthesis gas containing carbon oxides and hydrogen, substitute natural gas. In particular, the invention is directed to reducing the need for recirculation gas and the elimination of the respective drawbacks still affecting the known methods.

The basic idea of the invention consists in the parallel supply of fresh conditioned synthesis gas in the reactor section mahanirvana. The mentioned problem is solved by the method of production of CYP fresh raw synthesis gas, which comprises the step response of fresh synthesis gas in section mahanirvana, consisting of at least the first adiabatic reactor and other adiabatic reactor(s), connected in series in such a way that in each of the other reactor(s) enters the gas stream selected from the previous reactor section mahanirvana, and the step of recycling at least part of the reaction gas fed to one of the reactors. The method differs in that fresh raw synthesis gas are served in parallel in the above-mentioned reactors.

In a preferred embodiment, conditioned fresh raw synthesis gas is divided into several fresh gas flows, each of which is received in a corresponding one of the mentioned reactor section mahanirvana. More preferably, each of the fresh gas flow is 15-35% of the total flow of synthesis gas.

A typical device consists of four main reactors, connected in parallel, the following separation of flows of fresh standard gas: 25% goes to the first reactor 20% second 25% third and 30% in the fourth. The number of reactors depends on the type of catalyst (maximum outlet temperature) and the required quality of the gas (the maximum number of CO2and H2).

According to another variant of the invention, the recirculation gas is carried out by selection of the gas stream at the outlet of the first reactor and feeding the said part in the first reactor. In other words, in accordance with said another variant of the invention, the gas recirculation circuit includes only the first reactor, which serves fresh synthesis gas with the addition of recycled reaction gas, while in each of the second and other reactors fresh synthesis gas with the addition of the reaction gas from the previous reactor section mahanirvana.

In accordance with other vari is nami invention on the input of at least the first reactor and preferably also to the input of the second reactor section mahanirvana serves pairs. The addition of steam is effective in regulating the reaction temperature, as couples, as one of the products of reactions (I) and (II), diluted with fresh synthesis gas and shifts the chemical equilibrium, reducing the rate of the reaction inside the reactor.

In a preferred embodiment, the reaction gas from the first reactor is divided into first and second parts of the gas, the first part is recycled to dilute the flow of fresh gas fed to the first reactor to obtain a diluted gas stream inlet in said first reactor, which is then diluted by the addition of the steam flow before entry into the first reactor; the second part of the gas used to dilute the fresh gas fed to the second reactor section mahanirvana, the gas stream is included in the second reactor, also diluted with steam. Steam may be added before or after the dilution of the fresh gas recirculating or reactive gas.

In the present invention it is also proposed section mahanirvana for the conversion of synthesis gas containing carbon oxides and hydrogen, substitute natural gas, operating according to the above method, and installation, which includes a section mahanirvana.

In one embodiment of the invention section mahanirvana includes a first reactor and other reactors for carrying out mahanirvana fresh synthesis gas is a line of fresh synthesis gas in parallel in a first reactor, each reactor receives a share of the fresh synthesis gas.

In the preferred embodiment, includes a recirculation circuit, the receiving part of the reaction gas selected from the first reactor, and mixing this part of the reaction gas with a portion of fresh synthesis gas fed to the first reactor. More preferably, the offered line add the pair to further dilution gas included in the first and second reactor sections mahanirvana.

The invention has the following advantages. Since the first reactor receives only part of the raw fresh gas, the temperature inside the reactor can be controlled by using a lower ratio of recycle gas in comparison with the prior art, for example, when the molar ratio of total gas to fresh gas, equal to about 2. In addition, the need for recirculation of the reaction gas is reduced by the addition of steam at the preferred embodiments of the invention. Every second and other reactors receive part of the fresh gas diluted partially converted gas from the upstream reactor section mahanirvana, thus eliminating the need for recirculation of the gas in the reactor.

Thanks to the invention, the compressor in the recirculation circuit is much smaller than that required in the known level of those who IKI. For example, the plant operating prior art, performance CYP 2×106nm3/day, and typically requires a compressor with a capacity of 8 MW for recirculation of gas, while at the facility, working on the proposed method with the same performance, you will need a cheaper compressor 350 kW.

Another advantage is that due to separation of the fresh gas flow and the decrease in the recirculation gas, the gas flow in the reactor section mahanirvana reduced and, in particular, at the inlet of the first compressor. Thus, the invention allows the use of smaller aggregates and reduce the amount of catalyst in each reactor.

It should be noted that the invention does not affect the heat recovery, that is, the generation of superheated high pressure steam is the same as in methods based on the known state of the art.

All the above advantages make the RPG more competitive compared with fossil natural gas or other fuels. The invention is particularly useful for the production of CYP from biomass or coal gasification.

Other features and advantages of the present invention will be more apparent from the following description of a preferred, illustrative, and not limiting the scope of invention examples ssy is coy to the accompanying drawings.

Brief description of drawings

Attached to the description of the figure shows a diagram of the facility working on invented method.

A detailed description of the preferred option

Figure 1 is a section mahanirvana for the production of CYP specified number 10 in section receives raw 11 - fresh synthesis gas containing carbon oxides and hydrogen. Thread 11 fresh synthesis gas may be, for example, obtained in section gasification of coal or biomass (not shown).

Section 10 mahanirvana includes a series of adiabatic reactors 101-104 with heat recovery in heat exchangers 201-204. Known reactors 101-104, for example, with axial or axial-radial flow with an appropriate catalyst, working at a pressure of about 35 bar with the gas temperature at the inlet 240-300°C and the yield of about 600°C. In the heat exchangers 201-204 receives hot gas from the reactor 101-104, respectively, they can work as high-pressure steam boilers or, if necessary, to provide hot water or steam superheat. Line heat exchangers 201-204 hot water/steam in the drawing for simplicity is not shown.

As you can see, the thread 11 synthesis gas is fed in parallel to the reactor 101-104. Line feed synthesis gas section 10 mahanirvana provides separation of stream 11 stream 12 entering the first reactor 101, and the thread 13, which is further divided into threads 14, 15 & 16, sent to the reactor 102, 103 and 104, respectively. In a preferred embodiment of the invention the molar flow rate of gas in each of the gas streams 12-16 is 15-35% of the total flow 11 raw synthesis gas.

The gas flow 12 is diluted with a recycle gas stream 24 before entering the first reactor 101 and is sent to the heater 17. In this example, the obtained diluted and heated stream 18 is mixed with steam from line 19 for further dilution of fresh synthesis gas and then injected into the reactor 101.

The gas stream 20 from the reactor 101, partially converted to methane at high temperature, for example 600°C due to the exothermic reactions of mahanirvana, cooled in heat exchanger 201 to receive the cooled flow of the reactive gas 21.

The first part 22 of the mentioned thread 21 of the cooled recycle gas to the reactor 101 to the circuit 40 recirculation, includes a compressor 23.

On closer examination, the gas stream 22 is passed through a heater 17 for heating the gas stream entering the reactor 101, and is directed to the compressor 23. Thread 24 recirculating gas supplied by a compressor 23, as mentioned above, is used to dilute part of the fresh synthesis gas 12, which is directed to the reactor 101.

In a preferred embodiment, the ratio of the current flow 18, included in the first reactor 101, and a gas stream 12 flowing in the same reactor 101, equal to about 2 mol/mol.

The second part 25 of the stream 21 exiting the first reactor, mixed with fresh conditioned gas stream 14 with the further addition of a pair of line 26 to receive the diluted gas stream 27 coming in the second reactor 102. The gas flow 28 from the second reactor 102 is cooled in the heat exchanger 202, the cooled gas stream 29 enters the third reactor 103 together with the fresh gas flow 15. Similarly, the cooled gas stream 30 from the reactor 103 is mixed with fresh gas 16 and served in the fourth reactor 104.

It should be noted that the pairs can be added before or after the dilution of the fresh gas recirculating or reactive gas. In a preferred embodiment, pairs 19 is added to the diluted and heated stream 18, as shown; pairs 26 can be added to the fresh gas 14 or fresh gas 14, the diluted part 25 of the reaction gas.

The gas flow 32, extending from the fourth reactor 104, is cooled in heat exchanger 204 and sent to the separator 110 to the receiving stream 34 CYP and condensate 33; stream 34 CYP can be sent to other so-called reactor of the final product. Preferably the condensate drain 33 to feed CYP in the reactor of the final product in order to get more valuable konecne the th product.

CYP, as a rule, consists of not less than 95% methane (CH4with several percent of carbon dioxide, hydrogen and inert impurities. Received CYP can be used for any suitable purpose.

The following is a detailed description of the example. In section 10 mahanirvana, as can be seen from figure 1, flows 11 with a flow rate of 435,000 nm3/h fresh gas at 37°C, in the first reactor 101 enters the flow 12 flow 109,000 nm3/hour. The remainder is divided into streams of costs 88,000, 111,000 and 127,000 nm3per hour, received, respectively, in the reactor 102, 103 and 104. The steam flow with a flow rate of 35,000 kg/h at 450°C add lines 19, 20,000 kg/h of steam at the same temperature, add the line 26, while the flow 117,000 nm3/h diluted steam synthesis gas recycle line 22 and is connected with conditioned gas 12 in line 24. Get about 230,000 nm3per hour RPG in the form of a stream 34. The outlet temperature from the reactor to about 600°C.

Section 10 mahanirvana can be a Supplement to the installation for the production of CYP from an appropriate source such as coal or biomass; the installation may have other additions, for example, the gasifier, the installation of air separation, install the conversion of CO (water gas reaction) to provide the desired ratio between hydrogen and CO content of Sintez-gas, removal of acid gas, etc. it Should be noted that such components as valves, pumps, accessories, etc. are not shown because they are well known to specialists.

1. Method for the production of substitute natural gas (CYP) fresh raw synthesis gas (11), comprising at least steps of the reaction of fresh synthesis gas section (10) of mahanirvana containing at least the first adiabatic reactor (101) and at least an additional adiabatic reactor (102-104), connected in series, so that each additional reactor (102-104) enters the gas stream is taken from the previous reactor section mahanirvana, and recycling at least part (22) of the reaction gas as a gas inlet at least one of these reactors, characterized in that the fresh raw synthesis gas (11) simultaneously serves in the above-mentioned reactors (101-104), and the recirculation gas is conducted through the selection part (22) of the reaction gas flow (20) of the first reactor (101) and use that part (22) gas as a recirculation gas for diluting the stream (12) fresh gas entering the first reactor (101)receiving stream (18) diluted gas entering the first reactor.

2. The method according to claim 1, in which the mentioned fresh raw synthesis gas (11) is divided into the poison fresh gas flow (12, 14, 15, 16), each of which is served in a corresponding one of the reactors (101-104).

3. The method according to claim 2, in which use the partition (10) mahanirvana containing a few mentioned more adiabatic reactors (102-104), and each of the fresh gas flow (12, 14, 15, 16) is 15-35 mol.% of the total flow (11) of the gas.

4. The method according to claim 1, in which part (22) of the flow of the reaction gas fed to the inlet of the first reactor (101) in a recirculation circuit (40)includes a compressor (23) for the recirculating gas stream (22) and the heater (17) for heating the aforementioned diluted gas stream before entry into the first reactor (101).

5. The method according to claim 1, in which the molar ratio between the total flow (18) diluted gas within the first reactor (101), and stream (12) fresh gas entering the first reactor (101)is approximately 2.

6. The method according to claim 1, wherein the input of at least the first reactor (101) add steam for a further dilution of the incoming gas.

7. The method according to claim 6, in which the reaction gas (21) of the first reactor (101) is divided into a first part (22) and the second part (25), and the first part (22) recycle to dilute the fresh gas flow (12)received in the first reactor (101), with the diluted gas stream (18) at the entrance to the first reactor, referred to dilute the gas flux is (18) is further diluted by the addition of flow (19) steam prior to being fed into the first reactor (101), and the second part of the strip (25) is used for dilution of the fresh gas (14)received in the second reactor (102) of section (10) of mahanirvana, and gas flow incoming to the second reactor (102), then diluted with steam (26).

8. The method according to any of the preceding paragraphs, in which the reactors operating under a pressure of about 35 bar.

9. Section (10) of mahanirvana for the conversion of synthesis gas (11) to substitute natural gas (31), containing carbon dioxide and hydrogen according to the method according to any one of claims 1 to 8, comprising a first reactor (101) and a few additional reactors (102-104), adapted for the reaction metaniobate fresh synthesis gas (11), a line of fresh synthesis gas, providing parallel flow of fresh synthesis gas (11) in the first and additional reactors, each reactor receives a certain portion (12, 14, 15, 16) to the fresh synthesis gas, and a circuit (40) recycling, where does the part (22) of the reaction gas (21), taken from the first reactor (101), and mixed with part (12) of fresh synthesis gas entering the first reactor (101), and the gas recirculation circuit includes only the first reactor (101).

10. Section mahanirvana according to claim 9, which includes the line feed pair (19, 26) for subsequent dilution gas included in the first and second reactor sections mahanirvana.

11. Section mahanirvana who according to claim 9, includes four reactors (101-104), and fresh conditioned gas raw material (11) is divided into sections so that 25% is fed into the first reactor (101), 20% - in the second reactor (102), 25% in the third reactor (103) and 30% in the fourth reactor (104).

12. Section mahanirvana according to any one of the preceding paragraphs, including adiabatic reactors (101-104) with axial or axial-radial flow.



 

Same patents:

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FIELD: chemistry.

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5 cl, 2 dwg, 1 tbl, 9 ex

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16 cl, 1 tbl, 6 ex

FIELD: chemistry.

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79 cl, 4 ex, 18 dwg

FIELD: chemistry.

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4 cl, 1 tbl, 5 ex

FIELD: chemistry.

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EFFECT: invention is used to obtain a diesel fraction without further processing of the product.

38 cl, 8 tbl, 12 ex, 11 dwg

FIELD: power engineering.

SUBSTANCE: in a solar concentrator they carry out separately simultaneous stepwise heating of water steam and its mixture with a methane-containing gas, which is then sent to a reaction of steam catalytic conversion of the methane-containing gas into a sectioned catalytic reactor, installed outside the solar concentrator, the flow rate of water steam and its mixture with the methane-containing gas is reduced as the solar energy flow is reducing.

EFFECT: using this method makes it possible to reduce thermal costs for the process of energy resources generation and also to efficiently supply various energy resources under conditions of unavailability of methane sources, and also in the period of solar energy flow reduction at night time and when cloudiness increases.

8 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst for selective synthesis of high-quality gasoline fractions from synthesis gas and a method for production thereof. Described is a highly selective catalyst for producing high-quality gasoline fractions from synthesis gas, which consists of cobalt, a promoter and a molecular sieve, wherein the weight content of cobalt is 1-30%, the weight content of the promoter is 0.01-5%, and the remaining part is a molecular sieve, with respect to the weight of the catalyst, wherein the molecular sieve is one or more molecular sieves selected from molecular sieves Beta, ZSM-5, MOR, Y and MCM-22, wherein acidity of the molecular sieve is expressed through the amount of adsorbed NH3, and the adsorption capacity of the molecular sieve ranges from 0.16 to 0.50 mmol NH3/g; the molecular sieve has a microporous-mesoporous structure, wherein the micropores have diameter of 0.4-0.9 nm, and the mesopores have diameter of 2-30 nm, the specific surface area of the molecular sieve is 100-900 m2/g and the volume of micropores and mesopores is 0.1-0.6 cm3/g, respectively. Described is a method of producing a highly selective catalyst used for synthesis of high-quality gasoline fractions from synthesis gas by Fischer-Tropsch synthesis, involving the following steps: (1) preparing a weighed portion of a cobalt salt according to content of components given above, mixing with a solvent which is deionised water, alcohol or a ketone, to obtain a solution which contains a cobalt salt with concentration of 0.5-20 wt %; (2) preparing a weighed portion of a promoter according to content of components established above, adding to the prepared solution a cobalt salt and stirring for 0.5-3 hours; (3) preparing a weighed portion of a molecular sieve according to content of components established above, adding the molecular sieve to the prepared solution of cobalt salt, stirring for 0.1-15 hours and holding for 0.1-24 hours; (4) evaporating the suspension at temperature of 40-100°C and drying the obtained solid substance under a vacuum at temperature of 30-100°C for 1-24 hours; (5) calcining the dried substance on air at temperature of 300-550°C for 2-10 hours; (6) moulding the calcined powder as a catalyst precursor; (7) reducing the catalyst precursor in a hydrogen atmosphere or a mixture of hydrogen and an inert gas at temperature of 300-550°C for 1-10 hours.

EFFECT: described is a highly selective catalyst for producing high-quality gasoline fractions from synthesis gas.

13 cl, 17 tbl, 16 ex

FIELD: chemistry.

SUBSTANCE: invention relates to Fischer-Tropsch synthesis catalysts. Described is a method of producing a precursor of a cobalt-containing Fischer-Tropsch synthesis catalyst, which involves adding a polyfunctional carboxylic acid of general formula HOOC-C*R1C*R2~COOH(1) where, C* in each of the groups C*R1 and C*R2 is a sp2-hybridised carbon atom and R1 and R2 are identical or different and each is selected from a group consisting of hydrogen and alkyl which contains not more than six carbon atoms, into and/or onto catalyst support particles, with the ratio of the amount of the polyfunctional carboxylic acid and the size of the surface of the support in the range of 0.3-10 mcmol of carboxylic acid/m2 of the surface of the support; while adding carboxylic acid into and/or onto the catalyst support particles or after, simultaneously adding a cobalt compound into and/or onto the catalyst support particles and calcining the saturated support to form a precursor of a cobalt-containing Fischer-Tropsch synthesis catalyst.

EFFECT: described is a method of producing a Fischer-Tropsch synthesis catalyst which involves reduction of a catalyst precursor obtained using the described method; described is a method of producing hydrocarbons, which involves bringing into contact synthesis gas which contains hydrogen (H2) and carbon monoxide (CO), at high temperature of 80°C-250°C and high pressure of 10-40 bar with a Fischer-Tropsch synthesis catalyst obtained using said method, and a Fischer-Tropsch reaction between hydrogen and carbon monoxide.

17 cl; 2 dwg; 4 tbl; 7 ex

FIELD: hydrocarbon manufacturing.

SUBSTANCE: natural gas is brought into reaction with vapor and oxygen-containing gas in at least one reforming zone to produce syngas mainly containing hydrogen and carbon monoxide and some amount of carbon dioxide. Said gas is fed in Fisher-Tropsh synthesis reactor to obtain crude synthesis stream containing low hydrocarbons, high hydrocarbons, water, and unconverted syngas. Then said crude synthesis stream is separated in drawing zone onto crude product stream containing as main component high hydrocarbons, water stream, and exhaust gas stream, comprising mainly remained components. Further at least part of exhaust gas stream is vapor reformed in separated vapor reforming apparatus, and reformed exhaust gas is charged into gas stream before its introducing in Fisher-Tropsh synthesis reactor.

EFFECT: increased hydrocarbon yield with slight releasing of carbon dioxide.

7 cl, 3 dwg, 1 tbl, 5 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: fischer-Tropsch process catalyst constituted by cobalt deposited on aluminum metal may additionally contain promoters selected from oxides ZrO2, La2O3, K2O and metals Re, Ru, Pd, and Pt.

EFFECT: increased heat conductivity and selectivity.

2 cl, 2 tbl, 2 ex

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