CN105399604A - Energy-efficient super-large scale methanol-synthesizing method with production of steam of different grades and apparatus thereof - Google Patents

Abstract

The invention discloses an energy-efficient super-large scale methanol-synthesizing method with production of steam of different grades. Virgin gas is compressed and mixed with circulation gas for forming a gas mixture, the gas mixture is heated and simultaneously enters two parallelly arranged first methanol reactors for carrying out methanol synthesis reactions, and incompletely reacted synthetic gas and a methanol steam mixture are formed; the incompletely reacted synthetic gas and the methanol steam mixture are cooled and enter a second methanol reactor for carrying out a methanol synthesis reaction to obtain a final product; the final product is cooled and separated, and parts of the separated gas is used as circulation gas; and liquid crude methanol enters a downstream rectification unit. The invention also discloses an apparatus for realizing the method. A reasonably configured heat exchanger network is used for improving conversion per pass and concentration of methanol at the outlet of the reactor maximally, and reducing recycle ratio and energy consumption, and producing steam of different grades; the low pressure steam can meet low pressure steam demands of the downstream methanol rectification unit.

Description

A kind of energy-saving ultra-large methane synthesizing method and device producing different grades steam

Technical field

The present invention relates to and prepare methyl alcohol technical field by the synthetic gas comprising hydrogen and oxycarbide, particularly a kind of energy-saving ultra-large methane synthesizing method and device producing different grades steam.

Background technology

Those skilled in the art are known to pass through (H ₂-CO ₂)/(CO+CO ₂) value is the Method and process of the synthetic gas catalyzed reaction methanol of about 2.0 ~ 2.1.

The future developments such as current methanol-fueled CLC production equipment maximizes towards scale, and per pass conversion is high, and energy recovery is reasonable, and beds has a narrow range of temperature, and synthesis reactor pressure drop is little, and structure is simple, stable operation reliably facilitates.

Prepare the method and system of methyl alcohol on a large scale described by CN102171171A, first the first pipe-type water-cooling reactor generation methanol-fueled CLC reaction is entered after virgin gas mixes with circulation gas, then the mixture of reacted synthetic gas and methanol steam enters air cooling reactor again, the gas mixture of virgin gas and circulation gas is used to cool the reaction heat of air cooling reactor, reacted mixture is after overcooling, enter gas-liquid separator, one gas isolated circulates again.Use air cooling reactor in this methanol synthesis loop, there is heat transfer efficiency lower, bed temperature is not easy to control, and likely occurs the situation of the methyl alcohol in process gas in beds condensation; Because capacity usage ratio is low, follow-up flow process air cooling, water-cooled load is caused to increase; And there is no thermal source due to air cooling reactor, the reaction heat of self is few, easily occurs that driving initial stage temperature rise rate is slow, the problems such as the recovery time is long.The method for gas-phase reaction that patent CN1989092B describes, mention a kind of large-scale methanol synthesis loop, that is: virgin gas and synthetic gas pass through preheating, first the methanol reactor generation methanol-fueled CLC reaction of the generation steam of First radial direction is entered, synthetic gas and methanol steam mixture are after overcooling and separation of methanol, and the methanol reactor generation methanol-fueled CLC that gas enters second radial generation steam after recompression and preheating reacts.Final unreacted synthetic gas and methanol steam, through overcooling laggard enter gas-liquid separator, the gas of separation circulates again.In above-mentioned extensive methanol synthesis loop, methanol sythesis reactor upper catalyst bed layer is in overtemperature state always, and hot(test)-spot temperature reaches as high as 309 DEG C, easily more than 309 DEG C during load adjustment, causes there is hidden danger during system heavy-duty service; The problems such as appearance system wax deposition is serious, and by product increases, and internal circulating load is large, and energy consumption of compressor is high.

Summary of the invention

One of technical problem to be solved by this invention is for the above-mentioned technical problem existing for existing preparation on a large scale in methanol technics and provides a kind of energy-saving ultra-large methane synthesizing method producing different grades steam.

Two of technical problem to be solved by this invention is to provide the device of the energy-saving ultra-large methane synthesizing method realizing above-mentioned production different grades steam.

As the energy-saving ultra-large methane synthesizing method of the production different grades steam of first aspect present invention, it is characterized in that virgin gas is mixed to form the first gas mixture with circulation gas after overdraft, first gas mixture synchronously enters in two the first methanol reactors in parallel and carries out the complete synthetic gas of methanol-fueled CLC reaction generation unreacted and methanol steam mixture after heating up, the synthetic gas that described unreacted is complete and methanol steam mixture are after cooling or after intersegmental condensation separation portion of product, enter the second methanol reactor proceed methanol-fueled CLC and be obtained by reacting final product, described final product is through refrigerated separation, isolated portion gas is as described circulation gas, liquid crude methyl alcohol enters downstream rectification cell.

In a preferred embodiment of the invention, described first methanol reactor is water-cooled methanol reactor.

In a preferred embodiment of the invention, some reaction tubess are configured with in described water-cooled methanol reactor, copper-based catalysts is configured with in described reaction tubes, described first gas mixture enters in described reaction tubes, there is methanol-fueled CLC reaction under copper-based catalysts katalysis in described reaction tubes, remove methyl alcohol by boiled water outside described reaction tubes and react the heat produced.

In a preferred embodiment of the invention, described second methanol reactor is the board-like synthetic tower of IMC isothermal catalyzer being loaded on the isothermal fixed-bed reactor between heat transfer tube or being loaded on by catalyzer outside plank that CN203227477U describes.

In a preferred embodiment of the invention, outside the heat transfer tube that the synthetic gas that unreacted is complete and methanol steam mixture enter into described isothermal fixed-bed reactor or outside the plank of the board-like synthetic tower of IMC isothermal, there is methanol-fueled CLC reaction under copper-based catalysts katalysis outside heat transfer tube or outside plank, remove methyl alcohol by boiled water inside heat transfer tube or inside plank and react the heat produced.

In a preferred embodiment of the invention, in described second methanol reactor, the flow direction of reactant gases is axial or radial.

In a preferred embodiment of the invention, the copper-based catalysts in described first methanol reactor is identical with the copper-based catalysts in the second methanol reactor, is high/low temperature active copper catalyst based.

In a preferred embodiment of the invention, the copper-based catalysts in described first methanol reactor is high temperature active copper-based catalysts, and the copper-based catalysts in described second methanol reactor is low temperature active copper-based catalysts.

In a preferred embodiment of the invention, the pressure of described virgin gas after overdraft is 7.4 ~ 8.1MPag.

In a preferred embodiment of the invention, described first gas mixture enters the temperature of the first methanol reactor in parallel after heating up is 210 DEG C ~ 230 DEG C.

In a preferred embodiment of the invention, each component content of described first gas mixture after heating up is H ₂be 40 ~ 70mol%; CO is 5 ~ 25mol%; CO ₂be 1 ~ 10mol%.

In a preferred embodiment of the invention, described first methanol reactor uses boiled water to remove methanol-fueled CLC reaction liberated heat.

In a preferred embodiment of the invention, described first methanol reactor sends the first liquid-vapor mixture, produces the middle pressure steam that a pressure is 2.2MPag ~ 2.7MPag after described first liquid-vapor mixture carries out vapor-liquid separation.

In a preferred embodiment of the invention, described reaction forms the temperature of the complete synthetic gas of unreacted and methanol steam mixture is 240 DEG C ~ 260 DEG C.

In a preferred embodiment of the invention, the synthetic gas that described unreacted is complete and the temperature of methanol steam mixture after cooling are 210 DEG C ~ 220 DEG C.

In a preferred embodiment of the invention, the synthetic gas that described unreacted is complete and methanol steam mixture and described first gas mixture carry out heat exchange.

In a preferred embodiment of the invention, after the synthetic gas that described unreacted is complete and methanol steam mixture and described first gas mixture carry out heat exchange, again after intersegmental condensation separation portion of product, then enter the second methanol reactor after carrying out heat exchange with final product and proceed methanol-fueled CLC and be obtained by reacting final product.

In a preferred embodiment of the invention, the synthetic gas that described unreacted is complete and methanol steam mixture and described circulation gas carry out heat exchange.

In a preferred embodiment of the invention, described second methanol reactor uses boiled water to remove methanol-fueled CLC reaction liberated heat.

In a preferred embodiment of the invention, described second methanol reactor sends the second liquid-vapor mixture, and it is the low-pressure steam of 1.1MPag ~ 1.7MPag that described second liquid-vapor mixture carries out producing a pressure after carbonated drink is separated.

In a preferred embodiment of the invention, described final product through cooled temperature be 30 DEG C ~ 45 DEG C.

In a preferred embodiment of the invention, heat exchange is carried out with described first gas mixture in described final product process of cooling.

In a preferred embodiment of the invention, the alcohol net value in described final product is 18 ~ 21mol%.

As the device of the energy-saving ultra-large methane synthesizing method of the above-mentioned production different grades steam of a second aspect of the present invention, comprising:

First refrigerating unit, described first refrigerating unit has the first gas mixture entrance, the first mixed gas outlet, the first final product entrance, the first final product outlet, wherein said first gas mixture entrance connects one end of a virgin gas transfer lime and one end of the first circulation gas transfer lime, described virgin gas transfer lime sends virgin gas here, and described first circulation gas transfer lime sends circulation gas here;

Two the first methanol reactors, the top of each the first methanol reactor is configured with the second gas mixture entrance, top is configured with the first liquid-vapor mixture outlet, bottom is configured with the first Separation of Water refluxing opening, bottom is configured with the complete synthetic gas of the first unreacted and methanol steam mixture outlet, and wherein each second gas mixture entrance is connected with the first mixed gas outlet in described first refrigerating unit by one first mixed gas pipeline;

One first vapour liquid separator, described first vapour liquid separator is at least configured with two the first liquid-vapor mixture entrances, two the first Separation of Water outlets and a middle pressure steam outlet, wherein two the first liquid-vapor mixture entrances to export with first liquid-vapor mixture on a corresponding methanol reactor top respectively by two first liquid-vapor mixture transfer limes and connect, and two the first Separation of Waters outlets connect with the first Separation of Water refluxing opening of corresponding methanol reactor bottom respectively by two first Separation of Water transfer limes; Middle pressure steam is sent in described middle pressure steam outlet;

One second methanol reactor, the top of described second methanol reactor is configured with the complete synthetic gas of first unreacted and methanol steam mixture inlet and two the second liquid-vapor mixtures outlets, bottom is configured with one first final product outlet and two the second Separation of Water refluxing openings, and the complete synthetic gas of described first unreacted and methanol steam mixture inlet are connected by synthetic gas that the first unreacted the is complete synthetic gas complete with the first unreacted bottom two the first methanol reactors with methanol steam mixture transfer lime and methanol steam mixture outlet; Described first final product outlet is connected with the first final product entrance in described first refrigerating unit by the first final product transfer lime;

One second vapour liquid separator, described second vapour liquid separator is at least configured with two the second liquid-vapor mixture entrances, two the second Separation of Water outlet and low-pressure steam outlet, wherein two the second liquid-vapor mixture entrances export respectively by the second liquid-vapor mixture that two second liquid-vapor mixture transfer limes are corresponding with described second methanol reactor and connect, two the second Separation of Water outlets connect respectively by the second Separation of Water refluxing opening that two second Separation of Water transfer limes are corresponding with described second methanol reactor, and described low-pressure steam outlet sends low-pressure steam;

Second refrigerating unit, described second refrigerating unit has the second final product entrance and the outlet of the second final product, and the second final product entrance is exported with the first final product in described first refrigerating unit by the second final product transfer lime and is connected;

3rd refrigerating unit, described 3rd refrigerating unit has the 3rd final product entrance and the outlet of the 3rd final product, and the 3rd final product entrance is exported with the second final product in described second refrigerating unit by the 3rd final product transfer lime and is connected;

One the 3rd gas-liquid separator, described 3rd gas-liquid separator has the 4th final product entrance, the first circulation gas outlet and separating liquid outlet, and wherein said 4th final product entrance is exported with the 3rd final product in described 3rd refrigerating unit by the 4th final product transfer lime and is connected; Described first circulation gas outlet connects one on the one hand and speeds to put pipe, is connected on the other hand by a recycle compressor with the other end of described first circulation gas transfer lime;

One reduced-pressure flash tank, described reduced-pressure flash tank has a separating liquid entrance, crude carbinol outlet and flashed vapour outlet, described separating liquid entrance is exported with the separating liquid on described 3rd gas-liquid separator by separating liquid transfer lime and is connected, described crude carbinol outlet exports crude carbinol, and flashed vapour is sent in described flashed vapour outlet.

In a preferred embodiment of the invention, described first refrigerating unit is gas-gas heat exchanger, and the second refrigerating unit is air cooler, and the 3rd refrigerating unit is water cooling heat exchanger.

In a preferred embodiment of the invention, also comprise the 4th refrigerating unit, described 4th refrigerating unit has the complete synthetic gas of the second unreacted and methanol steam mixture inlet, the synthetic gas that second unreacted is complete and methanol steam mixture outlet, 3rd gas mixture entrance or the second circulation gas entrance, 3rd mixed gas outlet or the outlet of the second circulation gas, the complete synthetic gas of described second unreacted and methanol steam mixture inlet are connected by synthetic gas that described second unreacted the is complete synthetic gas complete with the first unreacted bottom two the first methanol reactors with methanol steam mixture transfer lime and methanol steam mixture outlet, the complete synthetic gas of described second unreacted and methanol steam mixture outlet are connected by synthetic gas that the 3rd unreacted the is complete synthetic gas complete with the first unreacted of described second methanol reactor with methanol steam mixture transfer lime and methanol steam mixture inlet, described 3rd gas mixture entrance is connected with the first mixed gas outlet in described first refrigerating unit by the second mixed gas pipeline or the second circulation gas entrance is connected with described first circulation gas transfer lime by the second circulation gas transfer lime, described 3rd mixed gas outlet is connected with the second gas mixture entrance in two the first methanol reactors by the 3rd mixed gas pipeline or described second circulation gas exports to be connected by the 3rd circulation gas transfer lime with the second gas mixture entrance in two the first methanol reactors and to pass through the 3rd mixed gas pipeline and is connected with the second gas mixture entrance in two the first methanol reactors.

In a preferred embodiment of the invention, to connect in described virgin gas transfer lime a compressor.

In a preferred embodiment of the invention, described first methanol reactor is water-cooled methanol reactor.

In a preferred embodiment of the invention, some first reaction tubess are configured with in described water-cooled methanol reactor, copper-based catalysts is configured with in described first reaction tubes, described first gas mixture enters in described first reaction tubes, methanol-fueled CLC reaction occurs under the copper-based catalysts katalysis in described first reaction tubes, and described first reaction tubes is outer to be cooled by boiled water.

In a preferred embodiment of the invention, described second methanol reactor is the board-like synthetic tower of IMC isothermal catalyzer being loaded on the isothermal fixed-bed reactor between heat transfer tube or being loaded on by catalyzer outside plank that CN203227477U describes.

In a preferred embodiment of the invention, the reactant gases in described second methanol reactor flows to as axis or radial form.

In a preferred embodiment of the invention, the copper-based catalysts in described first methanol reactor is identical with the copper-based catalysts in the second methanol reactor, is high/low temperature active copper catalyst based.

In a preferred embodiment of the invention, the copper-based catalysts in described first methanol reactor is high temperature active copper-based catalysts, and the copper-based catalysts in described second methanol reactor is low temperature active copper-based catalysts.

In a preferred embodiment of the invention, described first refrigerating unit, the 4th refrigerating unit are gas-gas heat exchanger, and the second refrigerating unit is air cooler, and the 3rd refrigerating unit is water cooling heat exchanger.

Or, as the device of the energy-saving ultra-large methane synthesizing method of the above-mentioned production different grades steam of a second aspect of the present invention, comprising:

5th refrigerating unit, described 5th refrigerating unit has the complete synthetic gas of the complete synthetic gas of the 4th gas mixture entrance, the 4th mixed gas outlet, the 3rd unreacted and methanol steam mixture inlet, the 3rd unreacted and methanol steam mixture outlet, wherein said 4th gas mixture entrance connects one end of a virgin gas transfer lime and one end of the first circulation gas transfer lime, described virgin gas transfer lime sends virgin gas here, and described first circulation gas transfer lime sends circulation gas here;

Two the first methanol reactors, the top of each the first methanol reactor is configured with the second gas mixture entrance, top is configured with the first liquid-vapor mixture outlet, bottom is configured with the first Separation of Water refluxing opening, bottom is configured with the complete synthetic gas of the first unreacted and methanol steam mixture outlet, and wherein each second gas mixture entrance is connected with the 3rd mixed gas outlet in described 5th refrigerating unit by one first mixed gas pipeline; The complete synthetic gas of the first unreacted bottom two the first methanol reactors is connected by the synthetic gas that the 4th unreacted the is complete synthetic gas complete with the 3rd unreacted of described 5th refrigerating unit with methanol steam mixture transfer lime and methanol steam mixture inlet with methanol steam mixture outlet and after connecing;

One first vapour liquid separator, described first vapour liquid separator is at least configured with two the first liquid-vapor mixture entrances, two the first Separation of Water outlets and a middle pressure steam outlet, wherein two the first liquid-vapor mixture entrances to export with first liquid-vapor mixture on a corresponding methanol reactor top respectively by two first liquid-vapor mixture transfer limes and connect, and two the first Separation of Waters outlets connect with the first Separation of Water refluxing opening of corresponding methanol reactor bottom respectively by two first Separation of Water transfer limes; Middle pressure steam is sent in described middle pressure steam outlet;

6th refrigerating unit, described 6th refrigerating unit has the complete synthetic gas of the complete synthetic gas of the 4th unreacted and methanol steam mixture inlet, the 4th unreacted and methanol steam mixture outlet, and the complete synthetic gas of the 4th unreacted of described 6th refrigerating unit and methanol steam mixture inlet are connected by synthetic gas that the 5th unreacted the is complete synthetic gas complete with the 3rd unreacted of described 5th refrigerating unit with methanol steam mixture transfer lime and methanol steam mixture outlet;

4th gas-liquid separation device, described 4th gas-liquid separation device has the complete synthetic gas of the 5th unreacted and the outlet of methanol steam mixture inlet, the complete syngas outlet of the first unreacted and the first separating liquid, and the complete synthetic gas of the 5th unreacted of described 4th gas-liquid separation device and methanol steam mixture inlet are connected by synthetic gas that the 6th unreacted the is complete synthetic gas complete with the 4th unreacted of described 6th refrigerating unit with methanol steam mixture transfer lime and methanol steam mixture outlet;

One second methanol reactor, the top of described second methanol reactor is configured with the complete synthetic gas entrance of first unreacted and two the second liquid-vapor mixtures outlets, and bottom is configured with one first final product outlet and two the second Separation of Water refluxing openings;

One second vapour liquid separator, described second vapour liquid separator is at least configured with two the second liquid-vapor mixture entrances, two the second Separation of Water outlet and low-pressure steam outlet, wherein two the second liquid-vapor mixture entrances export respectively by the second liquid-vapor mixture that two second liquid-vapor mixture transfer limes are corresponding with described second methanol reactor and connect, two the second Separation of Water outlets connect respectively by the second Separation of Water refluxing opening that two second Separation of Water transfer limes are corresponding with described second methanol reactor, and described low-pressure steam outlet sends low-pressure steam;

7th refrigerating unit, described 7th refrigerating unit has the 5th final product entrance, the 5th final product outlet, the second unreacted complete synthetic gas entrance, the complete syngas outlet of the second unreacted, 5th final product entrance of described 7th refrigerating unit is exported with the first final product bottom described second methanol reactor by the 5th final product transfer lime and is connected, and the second unreacted complete synthetic gas entrance of described 7th refrigerating unit is connected with the complete syngas outlet of the first unreacted of described 4th gas-liquid separation device by the first unreacted complete synthetic gas transfer lime; The complete syngas outlet of second unreacted of described 7th refrigerating unit is connected by the synthetic gas entrance that the second unreacted complete synthetic gas transfer lime is complete with first unreacted at described second methanol reactor top;

Second refrigerating unit, described second refrigerating unit has the second final product entrance and the outlet of the second final product, and the second final product entrance is exported with the 5th final product in described 7th refrigerating unit by the 6th final product transfer lime and is connected;

3rd refrigerating unit, described 3rd refrigerating unit has the 3rd final product entrance and the outlet of the 3rd final product, and the 3rd final product entrance is exported with the second final product in described second refrigerating unit by the 7th final product transfer lime and is connected;

One the 3rd gas-liquid separator, described 3rd gas-liquid separator has the 4th final product entrance, the first circulation gas outlet and the outlet of the second separating liquid, and wherein said 4th final product entrance is exported with the 3rd final product in described 3rd refrigerating unit by the 8th final product transfer lime and is connected; Described first circulation gas outlet connects one on the one hand and speeds to put pipe, is connected on the other hand by a recycle compressor with the other end of described first circulation gas transfer lime;

One reduced-pressure flash tank, described reduced-pressure flash tank has one the 3rd separating liquid entrance, crude carbinol outlet and flashed vapour outlet, described 3rd separating liquid entrance is exported with the second separating liquid on described 3rd gas-liquid separator by the first separating liquid transfer lime and is connected, described crude carbinol outlet exports crude carbinol, and flashed vapour is sent in described flashed vapour outlet;

8th refrigerating unit, described 8th refrigerating unit has the 4th separating liquid entrance, the 4th separating liquid outlet, described 4th separating liquid entrance is exported with the first separating liquid of described 4th gas-liquid separation device by the second separating liquid transfer lime and is connected, and the 4th separating liquid outlet of described 8th refrigerating unit is connected with described first separating liquid transfer lime by the 3rd separating liquid transfer lime.

In a preferred embodiment of the invention, to connect in described virgin gas transfer lime a compressor.

In a preferred embodiment of the invention, described first methanol reactor is water-cooled methanol reactor.

In a preferred embodiment of the invention, some first reaction tubess are configured with in described water-cooled methanol reactor, copper-based catalysts is configured with in described first reaction tubes, described first gas mixture enters in described first reaction tubes, methanol-fueled CLC reaction occurs under the copper-based catalysts katalysis in described first reaction tubes, and described first reaction tubes is outer to be cooled by boiled water.

In a preferred embodiment of the invention, described second methanol reactor is the board-like synthetic tower of IMC isothermal catalyzer being loaded on the isothermal fixed-bed reactor between heat transfer tube or being loaded on by catalyzer outside plank that CN203227477U describes.

In a preferred embodiment of the invention, the reactant gases in described second methanol reactor flows to as axis or radial form.

In a preferred embodiment of the invention, the copper-based catalysts in described first methanol reactor is identical with the copper-based catalysts in the second methanol reactor, is high/low temperature active copper catalyst based.

In a preferred embodiment of the invention, the copper-based catalysts in described first methanol reactor is high temperature active copper-based catalysts, and the copper-based catalysts in described second methanol reactor is low temperature active copper-based catalysts.

In a preferred embodiment of the invention, described second refrigerating unit is air cooler, and the 3rd refrigerating unit is water cooling heat exchanger, and the 5th refrigerating unit is gas-gas heat exchanger, the 6th refrigerating unit is air cooler, 7th refrigerating unit is gas-gas heat exchanger, and the 8th refrigerating unit is water cooling heat exchanger.

The present invention is configured by the flow process of above-mentioned methanol synthesis loop, can avoid the problem that prior art produces.And analyze from the chemical equilibrium angle of methanol-fueled CLC reaction, arrange like this and can improve per pass conversion and reactor outlet methanol concentration to greatest extent, reduce recycle ratio and energy consumption.

The present invention may be used for extensive methyl alcohol product installation (5500 tons/day or 1,800,000 tons/year), achieves the ultra-large methanol production of single series; Simultaneously the methanol synthesis loop of patent of the present invention can produce the steam of different grades, not only can beyond defeated middle pressure steam, and the demand for low pressure steam of downstream methanol rectifier unit can be met.The present invention can improve per pass conversion and reactor outlet methanol concentration to greatest extent, reduces recycle ratio and energy consumption.

Isothermal fixed-bed reactor or the board-like synthetic tower of IMC isothermal of water-cooled methanol reactor of the present invention and another kind of structure formation all use boiled water to remove heat of reaction, heat transfer efficiency is high, and Appropriate application heat of reaction, the low-pressure steam of generation is for downstream methanol rectifier unit.

The present invention compared with prior art, has following characteristics:

1. the present invention may be used for extensive methyl alcohol product installation, and the production capacity of methanol device can reach the ability of daily output 5500 tons/day or 1,800,000 tons/year.

2. the present invention is that first inlet tower gas enters two water-cooled methanol reactors in parallel, and reacted mixture enters the methanol reactor of an another kind of structure formation again, and proceed methanol-fueled CLC reaction, the alcohol net value that end reaction device is exported is high.From the chemical equilibrium angle of methanol-fueled CLC reaction, arrange like this and can improve per pass conversion and reactor outlet methanol concentration to greatest extent, reduce recycle ratio and energy consumption.

3. in synthesis loop of the present invention, can select according to actual condition, design two gas-gas heat exchanger series connection preheatings; The preheating of separate unit gas-gas heat exchanger or the gas mixture of two gas-gas heat exchangers to one circulation gas and circulation gas and virgin gas distinguish preheating.The optimization design of heat exchanger network can be realized, the rational and efficient use of energy in synthesis loop.

4. the methanol reactor of the another kind of structure formation of the present invention adopts the isothermal fixed-bed reactor structure formation be loaded on by catalyzer between heat transfer tube being similar to applicant's patent (grant number CN203227477U) and describing, or in this technical field the board-like synthetic tower structure of IMC isothermal that designs of the Casale that is familiar with.Copper-based catalysts is placed on outside pipe or plank, and synthetic gas carries out methanol-fueled CLC reaction outside reactor tube or plank.Use boiled water to remove reaction heat in reactor tube or plank, and produce low-pressure steam in drum.The low-pressure steam that isothermal methanol reactor of the present invention produces can meet the demand for low pressure steam of downstream methanol rectifier unit.

5, the reactant gases flow direction that the methanol reactor of another structure formation of the present invention can adopt can be axially or be radial form.

6, in the present invention, the methanol reactor of two water-cooled reactor and another structure formation can fill the copper-based catalysts of the same race simultaneously possessing high/low temperature activity; Respectively at two water-cooled reactor dress high temperature active copper-based catalysts, the copper-based catalysts of low temperature active can be filled at the methanol reactor of another structure formation.

7. in synthesis loop of the present invention, can select according to actual condition, design condensation separator between two water-cooled reactor series block, realize methyl alcohol and be separated with unreacted synthesis gas.Unreacted synthetic gas enters the methanol reactor of an another kind of structure formation, proceeds methanol-fueled CLC reaction.

Method and system of the present invention may be used for extensive methyl alcohol product installation, and throughput reaches daily output 5500 tons/day or 1,800,000 tons/year; Use water-cooled methanol reactor in parallel to connect the synthesis loop of isothermal methanol reactor of an another kind of structure formation producing steam, can produce the steam of different grades, low-pressure steam can meet the demand for low pressure steam of downstream methanol rectifier unit.By the heat exchanger network of reasonable disposition, improve per pass conversion and reactor outlet methanol concentration to greatest extent, reduce recycle ratio and energy consumption.

Accompanying drawing explanation

Fig. 1 is the energy-saving ultra-large methanol synthesizer schematic flow sheet that the embodiment of the present invention 1 produces different grades steam.

Fig. 2 is the energy-saving ultra-large methanol synthesizer schematic flow sheet that the embodiment of the present invention 2 produces different grades steam.

Fig. 3 is the energy-saving ultra-large methanol synthesizer schematic flow sheet that the embodiment of the present invention 3 produces different grades steam.

Fig. 4 is the energy-saving ultra-large methanol synthesizer schematic flow sheet that the embodiment of the present invention 4 produces different grades steam.

Embodiment

Embodiment 1

See Fig. 1, the energy-saving ultra-large methanol synthesizer of the production different grades steam provided in figure, comprises two water-cooled methanol reactors A1, A2, the methanol reactor C of an another kind of structure formation, two vapour liquid separators B, D, a gas-liquid separator H, a compressor K, two gas-gas heat exchangers L, E, an air cooler F, a water cooling heat exchanger G, a recycle compressor J, a reduced-pressure flash tank I.

Water-cooled methanol reactor A1, A2 top is configured with gas mixture entrance A11, A21, top is configured with liquid-vapor mixture outlet A12, A22, bottom is configured with Separation of Water refluxing opening A13, A23, bottom is configured with the complete synthetic gas of unreacted and methanol steam mixture outlet A14, A24, is also configured with goes into operation with heating unit A15, A25 in water-cooled methanol reactor A1, A2 bottom.Be configured with some reaction tubess in water-cooled methanol reactor A1, A2, in reaction tubes, be configured with copper-based catalysts, outside reaction tubes, pass through water cooling.

The methanol reactor C of another kind of structure formation is the board-like synthetic tower of IMC isothermal catalyzer being loaded on the isothermal fixed-bed reactor between heat transfer tube or being loaded on by catalyzer outside plank that CN203227477U describes.Water cooling is passed through in heat transfer tube or plank.Be configured with the complete synthetic gas of unreacted and methanol steam mixture inlet C1 and two liquid-vapor mixture outlet C2, C3 at the top of the methanol reactor C of another kind of structure formation, bottom is configured with a final product outlet C6 and two Separation of Water refluxing opening C4, C5.

Vapour liquid separator B is at least configured with two liquid-vapor mixture entrance B1, B2, two Separation of Water outlet B3, B4 and a middle pressure steam outlet B5.

Vapour liquid separator D is at least configured with two liquid-vapor mixture entrance D1, D2, two Separation of Water outlet D3, a D4 and low-pressure steam outlet D5.

Gas-liquid separator H has final product entrance H1, circulation gas outlet H2 and separating liquid outlet H3.

Gas-gas heat exchanger L has the complete synthetic gas of the complete synthetic gas of unreacted and methanol steam mixture inlet L1, unreacted and methanol steam mixture outlet L2, gas mixture entrance L3, mixed gas outlet L4.

Gas-gas heat exchanger E has gas mixture entrance E1, mixed gas outlet E2, final product entrance E3, final product outlet E4.

Reduced-pressure flash tank I has a separating liquid entrance I1, crude carbinol outlet I2 and flashed vapour outlet I3.

Virgin gas transfer lime 1 to be connected with the gas mixture entrance E1 of gas-gas heat exchanger E after connecing with circulation gas transfer lime 2 after compressors in series K, the mixed gas outlet E2 of gas-gas heat exchanger E is connected with the gas mixture entrance L3 of gas-gas heat exchanger L by mixed gas pipeline 3a, the mixed gas outlet L4 of gas-gas heat exchanger L is connected with gas mixture entrance A11, the A21 at water-cooled methanol reactor A1, A2 top by mixed gas pipeline 3, water-cooled methanol reactor A1, A2 parallel running.

Liquid-vapor mixture outlet A12, the A22 on water-cooled methanol reactor A1, A2 top are connected with two on vapour liquid separator B liquid-vapor mixture entrance B1, a B2 respectively by liquid-vapor mixture transfer lime 13,13a, and two Separation of Water outlets B3, B4 on vapour liquid separator B are connected with Separation of Water refluxing opening A13, A23 of water-cooled methanol reactor A1, A2 bottom by Separation of Water transfer lime 14,14a.

Water-cooled methanol reactor A1, the synthetic gas that unreacted bottom A2 is complete and methanol steam mixture outlet A14, A24 by the complete synthetic gas of unreacted and methanol steam mixture transfer lime 4 and gas-gas heat exchanger L there is the complete synthetic gas of unreacted and methanol steam mixture inlet L1 is connected, the have complete synthetic gas of unreacted and the methanol steam mixture outlet L2 of gas-gas heat exchanger L are connected by synthetic gas that unreacted the is complete synthetic gas complete with the unreacted at the methanol reactor C top of another kind of structure formation with methanol steam mixture transfer lime 5 and methanol steam mixture inlet C1.

Two liquid-vapor mixture outlets C2, the C3 at the methanol reactor C top of another kind of structure formation are connected with two liquid-vapor mixture entrances D1, D2 of vapour liquid separator D respectively by vapour-liquid transfer lime 15,15a, and two Separation of Water outlets D3, D4 of vapour liquid separator D are connected with two Separation of Water refluxing openings C4, C5 bottom the methanol reactor C of another kind of structure formation respectively by Separation of Water transfer lime 16,16a.

Final product outlet C6 bottom the methanol reactor C of another kind of structure formation is connected with the final product entrance E3 of gas-gas heat exchanger E by final product transfer lime 6, the final product outlet E4 of gas-gas heat exchanger E is connected with the entrance of air cooler F by final product transfer lime 7, the outlet of air cooler F is connected by the entrance of final product transfer lime 8 with water cooling heat exchanger G, and the outlet of water cooling heat exchanger G is connected with the final product entrance H1 of gas-liquid separator H by final product transfer lime 9.

Circulation gas outlet H2 mono-aspect of gas-liquid separator H is connected with the one end of speeding to put pipe 10, be connected with the entrance of recycle compressor J on the other hand, the outlet of recycle compressor J is connected with the other end of circulation gas transfer lime 2, the separating liquid outlet H3 of gas-liquid separator H is connected crude carbinol transfer lime 11 and flashed vapour outlet pipe 12 by the crude carbinol outlet I2 of the connection separating liquid entrance I1 of separating liquid transfer lime 17 with reduced-pressure flash tank I, reduced-pressure flash tank I respectively with flashed vapour outlet I3.

Virgin gas enters compressor K by virgin gas transfer lime 1, and pressure is increased to 7.4 ~ 8.1MPag, then mixes with the circulation gas from circulation gas transfer lime 2, mixed gas through gas-gas heat exchanger E, preheating mixture temperature to 180 DEG C ~ 200 DEG C.Gas mixture after preheating pre-heating temperature elevation to 210 DEG C ~ 230 DEG C again in gas-gas heat exchanger L.Inlet tower gas after intensification is entered in two water-cooled methanol reactors A1, A2 in parallel by mixed gas pipeline 3 uniformly distributing.In inlet tower gas, H2 is 40 ~ 70mol%; CO is 5 ~ 25mol%; CO2 is 1 ~ 10mol%.

Inlet tower gas enters in the reaction tubes of two water-cooled methanol reactors A1, A2, in reaction tubes copper-based catalysts katalysis under occur methanol-fueled CLC reaction, concrete reaction formula is as follows:

$\begin{array}{cc}CO+2H_2\⇔{\mathrm{CH}}_{3}OH& {\mathrm{CO}}_2+3H_2\⇔{\mathrm{CH}}_{3}OH+H_{2}O\end{array}$

Outside the pipe of the reaction tubes of two water-cooled methanol reactors A1, A2, use boiled water to remove methanol-fueled CLC reaction liberated heat, steam water interface enters vapour liquid separator B by liquid-vapor mixture transfer lime 13,13a simultaneously.The separation of liquid-vapor mixture is carried out and the middle pressure steam producing 2.2MPag ~ 2.7MPag delivers to full factory steam pipe system by the middle pressure steam outlet B5 on vapour liquid separator B in vapour liquid separator B.

The Separation of Water that vapour liquid separator B is separated enters into two water-cooled methanol reactor A1, A2 internal recycle respectively by Separation of Water transfer lime 14,14a and uses.

Through the complete synthetic gas of two water-cooled methanol reactor A1, A2 unreacteds in parallel and methanol steam mixture, temperature is at 240 DEG C ~ 260 DEG C.The synthetic gas complete by unreacted and methanol steam mixture transfer lime 4 enter gas-gas heat exchanger L, with the preheating material gas heat exchange come from gas-gas heat exchanger E in gas-gas heat exchanger L, after temperature is down to 220 DEG C ~ 210 DEG C.The synthetic gas that cooled unreacted is complete and methanol steam mixture enter the methanol reactor C of another kind of structure formation by the complete synthetic gas of unreacted and methanol steam mixture transfer lime 5, isothermal fixed-bed reactor catalyzer is loaded between heat transfer tube that the methanol reactor C of this another kind of structure formation can use Shanghai International Construction Engineering Consultation Corp.'s patent (grant number CN203227477U) to describe, or in this technical field the board-like synthetic tower structure of IMC isothermal that designs of the Casale that is familiar with.Outside the synthetic gas that unreacted is complete and the pipe that methanol steam mixture enters the methanol reactor C of another kind of structure formation or plank, and under pipe or the catalyst based effect of plank copper outside, continue methanol-fueled CLC reaction occurs.Because the generation drum pressure in the methanol reactor C of another kind of structure formation is lower, make temperature of reaction lower than water-cooled methanol reactor A1, A2 temperature in parallel, thus in the thermodynamics analysis of building-up reactions, available gas reaction in the synthetic gas making unreacted complete and methanol steam mixture more complete, the methanol content of outlet is higher, and alcohol net value reaches 18 ~ 21mol%.Boiled water is used to remove reaction heat inside the pipe of the methanol reactor C of another kind of structure formation or plank, liquid-vapor mixture enters in vapour liquid separator D by vapour-liquid transfer lime 15,15a, in vapour liquid separator D, carry out vapor-liquid separation, and the low-pressure steam producing 1.1MPag ~ 1.7MPag is sent by the low-pressure steam outlet D5 of vapour liquid separator D.The temperature of reacted final product is that 210 DEG C ~ 230 DEG C methanol reactor C leaving another kind of structure formation enter gas-gas heat exchanger E by final product transfer lime 6 and cool, and the gas mixture in preheating gas-gas heat exchanger E.The flow direction of the reactant gases in methanol reactor C is axial or radial.And copper-based catalysts in two water-cooled methanol reactor A1, A2 in parallel is all identical with the copper-based catalysts in methanol reactor C, be high/low temperature active copper catalyst based.Or the copper-based catalysts in two water-cooled methanol reactor A1, A2 in parallel is high temperature active copper-based catalysts, and the copper-based catalysts in methanol reactor C is low temperature active copper-based catalysts.

Cooled final product enters air cooler F through final product transfer lime 7, and temperature is down to 60 DEG C ~ 80 DEG C, then enters water cooling heat exchanger G by final product transfer lime 8, is cooled to 30 DEG C ~ 45 DEG C in water cooling heat exchanger G.Cooled final product enters in gas-liquid separator H by final product transfer lime 9, carries out the separation of gas-liquid mixture.Gas after separation one put pipe 10 by speeding and carry out speeding to put; Another stock enters in recycle compressor J and compresses, and then to be mixed with virgin gas by circulation gas transfer lime 2 and again reacts.The liquid be separated enters the crude carbinol generated after reduced-pressure flash tank I carries out vacuum flashing and enters methanol tank or send into downstream methanol rectifier unit.

Embodiment 2

See Fig. 2, the energy-saving ultra-large methanol synthesizer of production different grades steam provided in figure and the difference of embodiment 1 are to eliminate gas-gas heat exchanger L, water-cooled methanol reactor A1, the synthetic gas that unreacted bottom A2 is complete and methanol steam mixture outlet A14, A24 directly passes through the complete synthetic gas of the unreacted synthetic gas complete with the unreacted at the methanol reactor C top of another kind of structure formation with methanol steam mixture transfer lime 4 and methanol steam mixture inlet C1 is connected, the mixed gas outlet E2 of gas-gas heat exchanger E is directly by mixed gas pipeline 3 and water-cooled methanol reactor A1, the gas mixture entrance A11 at A2 top, A21 connects.

Virgin gas enters compressor K by virgin gas transfer lime 1, and pressure is increased to 7.9MPag, then mixes with the circulation gas from circulation gas transfer lime 2, mixed gas through gas-gas heat exchanger E, preheating mixture temperature to 210 DEG C.Inlet tower gas after intensification is entered in two water-cooled methanol reactors A1, A2 in parallel by mixed gas pipeline 3 uniformly distributing.In inlet tower gas, H2 is 40 ~ 70mol%; CO is 5 ~ 25mol%; CO2 is 1 ~ 10mol%.

Inlet tower gas enters in the reaction tubes of two water-cooled methanol reactors A1, A2, in reaction tubes copper-based catalysts katalysis under occur methanol-fueled CLC reaction, concrete reaction formula is as follows:

$\begin{array}{cc}CO+2H_2\⇔{\mathrm{CH}}_{3}OH& {\mathrm{CO}}_2+3H_2\⇔{\mathrm{CH}}_{3}OH+H_{2}O\end{array}$

Outside the pipe of the reaction tubes of two water-cooled methanol reactors A1, A2, use boiled water to remove methanol-fueled CLC reaction liberated heat, steam water interface enters vapour liquid separator B by gas-liquid mixture transfer lime 13,13a simultaneously.The separation of liquid-vapor mixture is carried out and the middle pressure steam producing 2.5MPag delivers to full factory steam pipe system by the middle pressure steam outlet B5 on vapour liquid separator B in vapour liquid separator B.

The Separation of Water that vapour liquid separator B is separated enters into two water-cooled methanol reactor A1, A2 internal recycle respectively by Separation of Water transfer lime 14,14a and uses.

Through the complete synthetic gas of two water-cooled methanol reactor A1, A2 unreacteds in parallel and methanol steam mixture, temperature is at 250 DEG C.The synthetic gas complete by unreacted and methanol steam mixture transfer lime 4 enter the methanol reactor C of another kind of structure formation, isothermal fixed-bed reactor catalyzer is loaded between heat transfer tube that the methanol reactor C of this another kind of structure formation can use Shanghai International Construction Engineering Consultation Corp.'s patent (grant number CN203227477U) to describe, or in this technical field the board-like synthetic tower structure of IMC isothermal that designs of the Casale that is familiar with.Outside the synthetic gas that unreacted is complete and the pipe that methanol steam mixture enters the methanol reactor C of another kind of structure formation or plank, and under pipe or the catalyst based effect of plank copper outside, continue methanol-fueled CLC reaction occurs.Because the generation drum pressure in the methanol reactor C of another kind of structure formation is lower, make temperature of reaction lower than water-cooled methanol reactor A1, A2 temperature in parallel, thus in the thermodynamics analysis of building-up reactions, available gas reaction in the synthetic gas making unreacted complete and methanol steam mixture more complete, the methanol content of outlet is higher, and alcohol net value reaches 19.6mol%.Boiled water is used to remove reaction heat inside the pipe of the methanol reactor C of another kind of structure formation or plank, liquid-vapor mixture enters in vapour liquid separator D by vapour-liquid transfer lime 15,15a, in vapour liquid separator D, carry out vapor-liquid separation, and the low-pressure steam producing 1.45MPag is sent by the low-pressure steam outlet D5 of vapour liquid separator D.The temperature of reacted final product is that 223 DEG C of methanol reactor C leaving another kind of structure formation enter gas-gas heat exchanger E by final product transfer lime 6 and cool, and the gas mixture in preheating gas-gas heat exchanger E.The flow direction of the reactant gases in methanol reactor C is axial or radial.And copper-based catalysts in two water-cooled methanol reactor A1, A2 in parallel is all identical with the copper-based catalysts in methanol reactor C, be high/low temperature active copper catalyst based.Or the copper-based catalysts in two water-cooled methanol reactor A1, A2 in parallel is high temperature active copper-based catalysts, and the copper-based catalysts in methanol reactor C is low temperature active copper-based catalysts.

Cooled final product enters air cooler F through final product transfer lime 7, and temperature is down to 70 DEG C, then enters water cooling heat exchanger G by final product transfer lime 8, is cooled to 40 DEG C in water cooling heat exchanger G.Cooled final product enters in gas-liquid separator H by final product transfer lime 9, carries out the separation of gas-liquid mixture.Gas after separation one put pipe 10 by speeding and carry out speeding to put; Another stock enters in recycle compressor J and compresses, and then to be mixed with virgin gas by circulation gas transfer lime 2 and again reacts.The liquid be separated enters the crude carbinol generated after reduced-pressure flash tank I carries out vacuum flashing and enters methanol tank or send into downstream methanol rectifier unit.

Embodiment 3

See Fig. 3, the energy-saving ultra-large methanol synthesizer of production different grades steam provided in figure and the difference of embodiment 1 are that gas-gas heat exchanger L has the complete synthetic gas of unreacted and methanol steam mixture inlet L1, the synthetic gas that unreacted is complete and methanol steam mixture outlet L2, circulation gas entrance L3 ', circulation gas outlet L4 ', circulation gas transfer lime 2 is also connected with the circulation gas entrance L3 ' of gas-gas heat exchanger L by a circulation gas transfer lime 2a, the circulation gas outlet L4 ' of gas-gas heat exchanger L is by mixed gas pipeline 3 ' and water-cooled methanol reactor A1, the gas mixture entrance A11 at A2 top, A21 connects, the mixed gas outlet E2 of gas-gas heat exchanger E is by mixed gas pipeline 3 " be connected with mixed gas pipeline 3 '.

Virgin gas enters compressor K by virgin gas transfer lime 1, and pressure is increased to 7.9MPag, then mixes with one circulation gas from circulation gas transfer lime 2, mixed gas through gas-gas heat exchanger E, preheating mixture temperature to 205 DEG C.Another stock of circulation gas enters gas-gas heat exchanger L by circulation gas transfer lime 2a, temperature after preheating rises to 240 DEG C, circulation gas after preheating and the gas mixture after preheating mix again, temperature is down to 212 DEG C, and mixed inlet tower gas is entered in two water-cooled methanol reactors A1, A2 in parallel by mixed gas pipeline 3 ' uniformly distributing.In inlet tower gas, H2 is 40 ~ 70mol%; CO is 5 ~ 25mol%; CO2 is 1 ~ 10mol%.

Inlet tower gas enters in the reaction tubes of two water-cooled methanol reactors A1, A2, in reaction tubes copper-based catalysts katalysis under occur methanol-fueled CLC reaction, concrete reaction formula is as follows:

$\begin{array}{cc}CO+2H_2\⇔{\mathrm{CH}}_{3}OH& {\mathrm{CO}}_2+3H_2\⇔{\mathrm{CH}}_{3}OH+H_{2}O\end{array}$

Outside the pipe of the reaction tubes of two water-cooled methanol reactors A1, A2, use boiled water to remove methanol-fueled CLC reaction liberated heat, steam water interface enters vapour liquid separator B by liquid-vapor mixture transfer lime 13,13a simultaneously.The separation of gas-liquid mixture is carried out and the middle pressure steam producing 2.2MPag ~ 2.7MPag delivers to full factory steam pipe system by the middle pressure steam outlet B5 on vapour liquid separator B in vapour liquid separator B.

The Separation of Water that vapour liquid separator B is separated enters into two water-cooled methanol reactor A1, A2 internal recycle respectively by Separation of Water transfer lime 14,14a and uses.

Through the complete synthetic gas of two water-cooled methanol reactor A1, A2 unreacteds in parallel and methanol steam mixture, temperature is at 240 DEG C ~ 260 DEG C.The synthetic gas complete by unreacted and methanol steam mixture transfer lime 4 enter gas-gas heat exchanger L, with the circulation gas heat exchange brought from circulation gas transfer lime 2a in gas-gas heat exchanger L, after temperature is down to 205 DEG C.The synthetic gas that cooled unreacted is complete and methanol steam mixture enter the methanol reactor C of another kind of structure formation by the complete synthetic gas of unreacted and methanol steam mixture transfer lime 5, isothermal fixed-bed reactor catalyzer is loaded between heat transfer tube that the methanol reactor C of this another kind of structure formation can use Shanghai International Construction Engineering Consultation Corp.'s patent (grant number CN203227477U) to describe, or in this technical field the board-like synthetic tower structure of IMC isothermal that designs of the Casale that is familiar with.Outside the synthetic gas that unreacted is complete and the pipe that methanol steam mixture enters the methanol reactor C of another kind of structure formation or plank, and under pipe or the catalyst based effect of plank copper outside, continue methanol-fueled CLC reaction occurs.Because the generation drum pressure in the methanol reactor C of another kind of structure formation is lower, make temperature of reaction lower than water-cooled methanol reactor A1, A2 temperature in parallel, thus in the thermodynamics analysis of building-up reactions, available gas reaction in the synthetic gas making unreacted complete and methanol steam mixture more complete, the methanol content of outlet is higher, and alcohol net value reaches 20.3mol%.Boiled water is used to remove reaction heat inside the pipe of the methanol reactor C of another kind of structure formation or plank, liquid-vapor mixture enters in vapour liquid separator D by vapour-liquid transfer lime 15,15a, in vapour liquid separator D, carry out vapor-liquid separation, and the low-pressure steam producing 1.29MPag is sent by the low-pressure steam outlet D5 of vapour liquid separator D.The temperature of reacted final product is that 215 DEG C of methanol reactor C leaving another kind of structure formation enter gas-gas heat exchanger E by final product transfer lime 6 and cool, and the gas mixture in preheating gas-gas heat exchanger E.The flow direction of the reactant gases in methanol reactor C is axial or radial.And copper-based catalysts in two water-cooled methanol reactor A1, A2 in parallel is all identical with the copper-based catalysts in methanol reactor C, be high/low temperature active copper catalyst based.Or the copper-based catalysts in two water-cooled methanol reactor A1, A2 in parallel is high temperature active copper-based catalysts, and the copper-based catalysts in methanol reactor C is low temperature active copper-based catalysts.

Cooled final product enters air cooler F through final product transfer lime 7, and temperature is down to 70 DEG C, then enters water cooling heat exchanger G by final product transfer lime 8, is cooled to 40 DEG C in water cooling heat exchanger G.Cooled final product enters in gas-liquid separator H by final product transfer lime 9, carries out the separation of gas-liquid mixture.Gas after separation one put pipe 10 by speeding and carry out speeding to put; Another stock enters in recycle compressor J and compresses, and then to be mixed with virgin gas by circulation gas transfer lime 2 and again reacts.The liquid be separated enters the crude carbinol generated after reduced-pressure flash tank I carries out vacuum flashing and enters methanol tank or send into downstream methanol rectifier unit.

Embodiment 4

See the energy-saving ultra-large methanol synthesizer of the production different grades steam provided in Fig. 4, figure, comprise two water-cooled methanol reactors A1, A2, the methanol reactor C of an another kind of structure formation, two vapour liquid separators B, D, a gas-liquid separator H, one compressor K, two gas-gas heat exchanger L ', E ', an air cooler F, a water cooling heat exchanger G, a recycle compressor J, a reduced-pressure flash tank I, an air cooler M, a gas-liquid separator N, a water cooler P.

Water-cooled methanol reactor A1, A2 top is configured with gas mixture entrance A11, A21, top is configured with liquid-vapor mixture outlet A12, A22, bottom is configured with Separation of Water refluxing opening A13, A23, bottom is configured with the complete synthetic gas of unreacted and methanol steam mixture outlet A14, A24, is also configured with goes into operation with heating unit A15, A25 in water-cooled methanol reactor A1, A2 bottom.Be configured with some reaction tubess in water-cooled methanol reactor A1, A2, in reaction tubes, be configured with copper-based catalysts, outside reaction tubes, pass through water cooling.

The methanol reactor C of another kind of structure formation is the board-like synthetic tower of IMC isothermal catalyzer being loaded on the isothermal fixed-bed reactor between heat transfer tube or being loaded on by catalyzer outside plank that CN203227477U describes.Water cooling is passed through in heat transfer tube or plank.Be configured with synthetic gas entrance C1 ' and two liquid-vapor mixture outlet C2, C3 that a unreacted is complete at the top of the methanol reactor C of another kind of structure formation, bottom is configured with a final product outlet C6 and two Separation of Water refluxing opening C4, C5.

Vapour liquid separator B is at least configured with two liquid-vapor mixture entrance B1, B2, two Separation of Water outlet B3, B4 and a middle pressure steam outlet B5.

Vapour liquid separator D is at least configured with two liquid-vapor mixture entrance D1, D2, two Separation of Water outlet D3, a D4 and low-pressure steam outlet D5.

Gas-liquid separator H has final product entrance H1, circulation gas outlet H2 and separating liquid outlet H3.

Gas-gas heat exchanger L ' has the complete synthetic gas of the complete synthetic gas of unreacted and methanol steam mixture inlet L1 ', unreacted and methanol steam mixture outlet L2 ', gas mixture entrance L3 ', mixed gas outlet L4 '.

Gas-gas heat exchanger E ' has unreacted complete synthetic gas entrance E1 ', the complete syngas outlet E2 ' of unreacted, final product entrance E3 ', final product outlet E4 '.

Reduced-pressure flash tank I has a separating liquid entrance I1, crude carbinol outlet I2 and flashed vapour outlet I3.

Air cooler M has the complete synthetic gas of the complete synthetic gas of unreacted and methanol steam mixture inlet M1, unreacted and methanol steam mixture outlet M2.

Gas-liquid separator N has the complete synthetic gas of unreacted and methanol steam mixture inlet N1, the complete syngas outlet N2 of unreacted and separating liquid outlet N3.

Water cooling heat exchanger P has separating liquid entrance P1 and separating liquid outlet P2.

Virgin gas transfer lime 1 to be connected with the gas mixture entrance L3 ' of gas-gas heat exchanger L ' after connecing with circulation gas transfer lime 2 after compressors in series K, the mixed gas outlet L4 ' of gas-gas heat exchanger L is connected with gas mixture entrance A11, the A21 at water-cooled methanol reactor A1, A2 top by mixed gas pipeline 3b, water-cooled methanol reactor A1, A2 parallel running.

Liquid-vapor mixture outlet A12, the A22 on water-cooled methanol reactor A1, A2 top are connected with two on vapour liquid separator B liquid-vapor mixture entrance B1, a B2 respectively by liquid-vapor mixture transfer lime 13,13a, and two Separation of Water outlets B3, B4 on vapour liquid separator B are connected with Separation of Water refluxing opening A13, A23 of water-cooled methanol reactor A1, A2 bottom by Separation of Water transfer lime 14,14a.

Water-cooled methanol reactor A1, the synthetic gas that unreacted bottom A2 is complete and methanol steam mixture outlet A14, A24 by the complete synthetic gas of unreacted and methanol steam mixture transfer lime 4a and gas-gas heat exchanger L ' there is the complete synthetic gas of unreacted and methanol steam mixture inlet L1 ' is connected, the have complete synthetic gas of unreacted and the methanol steam mixture outlet L2 ' of gas-gas heat exchanger L ' are connected by synthetic gas that unreacted the is complete synthetic gas complete with the unreacted of air cooler M with methanol steam mixture transfer lime 4b and methanol steam mixture inlet M1, the complete synthetic gas of the unreacted of air cooler M and methanol steam mixture outlet M2 are connected by synthetic gas that unreacted the is complete synthetic gas complete with the unreacted of gas-liquid separator N with methanol steam mixture transfer lime 4c and methanol steam mixture inlet N1, the complete syngas outlet N2 of unreacted of gas-liquid separator N is connected with the unreacted of gas-gas heat exchanger E ' complete synthetic gas entrance E1 ' by unreacted complete synthetic gas transfer lime 18a, gas-gas heat exchanger E ' is had the complete syngas outlet E2 ' of unreacted and is connected by the synthetic gas entrance C1 ' that unreacted complete synthetic gas transfer lime 18b is complete with the unreacted at the methanol reactor C top of another kind of structure formation.

Two liquid-vapor mixture outlets C2, the C3 at the methanol reactor C top of another kind of structure formation are connected with two liquid-vapor mixture entrances D1, D2 of vapour liquid separator D respectively by vapour-liquid transfer lime 15,15a, and two Separation of Water outlets D3, D4 of vapour liquid separator D are connected with two Separation of Water refluxing openings C4, C5 bottom the methanol reactor C of another kind of structure formation respectively by Separation of Water transfer lime 16,16a.

Final product outlet C6 bottom the methanol reactor C of another kind of structure formation is connected with the final product entrance E3 ' of gas-gas heat exchanger E ' by final product transfer lime 6a, the final product outlet E4 ' of gas-gas heat exchanger E ' is connected with the entrance of air cooler F by final product transfer lime 6b, the outlet of air cooler F is connected by the entrance of final product transfer lime 8 with water cooling heat exchanger G, and the outlet of water cooling heat exchanger G is connected with the final product entrance H1 of gas-liquid separator H by final product transfer lime 9.

Circulation gas outlet H2 mono-aspect of gas-liquid separator H is connected with the one end of speeding to put pipe 10, be connected with the entrance of recycle compressor J on the other hand, the outlet of recycle compressor J is connected with the other end of circulation gas transfer lime 2, the separating liquid outlet H3 of gas-liquid separator H is connected crude carbinol transfer lime 11 and flashed vapour outlet pipe 12 by the crude carbinol outlet I2 of the connection separating liquid entrance I1 of separating liquid transfer lime 17 with reduced-pressure flash tank I, reduced-pressure flash tank I respectively with flashed vapour outlet I3.

The separating liquid outlet N3 of gas-liquid separator N is connected with the separating liquid entrance P1 of water cooling heat exchanger P by separating liquid transfer lime 19a, and the separating liquid outlet P2 of water cooling heat exchanger P is connected with separating liquid transfer lime 17 by separating liquid transfer lime 19b.

Virgin gas enters compressor K by virgin gas transfer lime 1, and pressure is increased to 7.9MPag, then mixes with the circulation gas from circulation gas transfer lime 2, mixed gas through gas-gas heat exchanger L ', preheating mixture temperature to 210 DEG C.Inlet tower gas after intensification and gas mixture are entered in two water-cooled methanol reactors A1, A2 in parallel by mixed gas pipeline 3b uniformly distributing.In inlet tower gas, H2 is 40 ~ 70mol%; CO is 5 ~ 25mol%; CO2 is 1 ~ 10mol%.

Inlet tower gas enters in the reaction tubes of two water-cooled methanol reactors A1, A2, in reaction tubes copper-based catalysts katalysis under occur methanol-fueled CLC reaction, concrete reaction formula is as follows:

$\begin{array}{cc}CO+2H_2\⇔{\mathrm{CH}}_{3}OH& {\mathrm{CO}}_2+3H_2\⇔{\mathrm{CH}}_{3}OH+H_{2}O\end{array}$

Outside the pipe of the reaction tubes of two water-cooled methanol reactors A1, A2, use boiled water to remove methanol-fueled CLC reaction liberated heat, steam water interface enters vapour liquid separator B by liquid-vapor mixture transfer lime 13,13a simultaneously.The separation of liquid-vapor mixture is carried out and the middle pressure steam producing 2.6MPag delivers to full factory steam pipe system by the middle pressure steam outlet B5 on vapour liquid separator B in vapour liquid separator B.

The Separation of Water that vapour liquid separator B is separated enters into two water-cooled methanol reactor A1, A2 internal recycle respectively by Separation of Water transfer lime 14,14a and uses.

Through the complete synthetic gas of two water-cooled methanol reactor A1, A2 unreacteds in parallel and methanol steam mixture, temperature is at 250 DEG C.The synthetic gas complete by unreacted and methanol steam mixture transfer lime 4a enter gas-gas heat exchanger L ', with the gas mixture heat exchange of circulation gas and unstripped gas in gas-gas heat exchanger L ', temperature is down to 140 ~ 130 DEG C, the synthetic gas that cooled unreacted is complete and methanol steam mixture enter air cooler M through the complete synthetic gas of unreacted and methanol steam mixture transfer lime 4b, temperature is down to 70 DEG C, enter in gas-liquid separator N by the complete synthetic gas of unreacted and methanol steam mixture transfer lime 4c again, carry out the separation of gas-liquid mixture.Liquid after separation enters water cooling heat exchanger P by separating liquid transfer lime 19a, in water cooling heat exchanger P, be cooled to 40 DEG C, then enter by separating liquid transfer lime 19b, separating liquid transfer lime 17 crude carbinol generated after reduced-pressure flash tank I carries out vacuum flashing and enter methanol tank or send into downstream methanol rectifier unit.

The complete synthetic gas of unreacted after separation enters gas-gas heat exchanger E ' by the synthetic gas transfer lime 18a that unreacted is complete, preheating mixture temperature to 210 DEG C, then the methanol reactor C of another kind of structure formation is entered by the synthetic gas transfer lime 18b that unreacted is complete, isothermal fixed-bed reactor catalyzer is loaded between heat transfer tube that the methanol reactor C of this another kind of structure formation can use Shanghai International Construction Engineering Consultation Corp.'s patent (grant number CN203227477U) to describe, or in this technical field the board-like synthetic tower structure of IMC isothermal that designs of the Casale that is familiar with.Outside the synthetic gas that unreacted is complete and the pipe that methanol steam mixture enters the methanol reactor C of another kind of structure formation or plank, and under pipe or the catalyst based effect of plank copper outside, continue methanol-fueled CLC reaction occurs.Because the generation drum pressure in the methanol reactor C of another kind of structure formation is lower, make temperature of reaction lower than water-cooled methanol reactor A1, A2 temperature in parallel, thus in the thermodynamics analysis of building-up reactions, available gas reaction in the synthetic gas making unreacted complete and methanol steam mixture more complete, the methanol concentration of outlet is 12.3mol%.Boiled water is used to remove reaction heat inside the pipe of the methanol reactor C of another kind of structure formation or plank, liquid-vapor mixture enters in vapour liquid separator D by vapour-liquid transfer lime 15,15a, in vapour liquid separator D, carry out vapor-liquid separation, and the low-pressure steam producing 1.29MPag is sent by the low-pressure steam outlet D5 of vapour liquid separator D.The temperature of reacted final product is that 225 DEG C of methanol reactor C leaving another kind of structure formation enter gas-gas heat exchanger E ' by final product transfer lime 6a and cool, and the gas mixture in preheating gas-gas heat exchanger E '.The flow direction of the reactant gases in methanol reactor C is axial or radial.And copper-based catalysts in two water-cooled methanol reactor A1, A2 in parallel is all identical with the copper-based catalysts in methanol reactor C, be high/low temperature active copper catalyst based.Or the copper-based catalysts in two water-cooled methanol reactor A1, A2 in parallel is high temperature active copper-based catalysts, and the copper-based catalysts in methanol reactor C is low temperature active copper-based catalysts.

Cooled final product enters air cooler F through final product transfer lime 6b, then enters water cooling heat exchanger G by final product transfer lime 8, is cooled to 40 DEG C in water cooling heat exchanger G.Cooled final product enters in gas-liquid separator H by final product transfer lime 9, carries out the separation of gas-liquid mixture.Gas after separation one put pipe 10 by speeding and carry out speeding to put; Another stock enters in recycle compressor J and compresses, and then to be mixed with virgin gas by circulation gas transfer lime 2 and again reacts.The liquid be separated enters the crude carbinol generated after reduced-pressure flash tank I carries out vacuum flashing and enters methanol tank or send into downstream methanol rectifier unit.

Claims (44)

1. produce the energy-saving ultra-large methane synthesizing method of different grades steam, it is characterized in that virgin gas is mixed to form the first gas mixture with circulation gas after overdraft, first gas mixture synchronously enters in two the first methanol reactors in parallel and carries out the complete synthetic gas of methanol-fueled CLC reaction generation unreacted and methanol steam mixture after heating up, the synthetic gas that described unreacted is complete and methanol steam mixture are after cooling or after intersegmental condensation separation portion of product, enter the second methanol reactor proceed methanol-fueled CLC and be obtained by reacting final product, described final product is through refrigerated separation, isolated portion gas is as described circulation gas, liquid crude methyl alcohol enters downstream rectification cell.

2. the energy-saving ultra-large methane synthesizing method producing different grades steam as claimed in claim 1, is characterized in that described first methanol reactor is water-cooled methanol reactor.

3. the energy-saving ultra-large methane synthesizing method producing different grades steam as claimed in claim 2, it is characterized in that being configured with some reaction tubess in described water-cooled methanol reactor, copper-based catalysts is configured with in described reaction tubes, described first gas mixture enters in described reaction tubes, there is methanol-fueled CLC reaction under copper-based catalysts katalysis in described reaction tubes, remove methyl alcohol by boiled water outside described reaction tubes and react the heat produced.

4. the energy-saving ultra-large methane synthesizing method producing different grades steam as claimed in claim 3, is characterized in that described second methanol reactor is the board-like synthetic tower of IMC isothermal catalyzer being loaded on the isothermal fixed-bed reactor between heat transfer tube or being loaded on by catalyzer outside plank that CN203227477U describes.

5. the energy-saving ultra-large methane synthesizing method producing different grades steam as claimed in claim 4, it is characterized in that outside the heat transfer tube that the synthetic gas that unreacted is complete and methanol steam mixture enter into described isothermal fixed-bed reactor or outside the plank of the board-like synthetic tower of IMC isothermal, there is methanol-fueled CLC reaction under copper-based catalysts katalysis outside heat transfer tube or outside plank, remove methyl alcohol by boiled water inside heat transfer tube or inside plank and react the heat produced.

6. the energy-saving ultra-large methane synthesizing method producing different grades steam as claimed in claim 5, it is characterized in that in described second methanol reactor, the flow direction of reactant gases is axial or radial.

7. the energy-saving ultra-large methane synthesizing method producing different grades steam as claimed in claim 5, it is characterized in that the copper-based catalysts in described first methanol reactor is identical with the copper-based catalysts in the second methanol reactor, be high/low temperature active copper catalyst based.

8. the energy-saving ultra-large methane synthesizing method producing different grades steam as claimed in claim 5, it is characterized in that the copper-based catalysts in described first methanol reactor is high temperature active copper-based catalysts, the copper-based catalysts in described second methanol reactor is low temperature active copper-based catalysts.

9. the energy-saving ultra-large methane synthesizing method producing different grades steam as claimed in claim 1, is characterized in that the pressure of described virgin gas after overdraft is 7.4 ~ 8.1MPag.

10. the as claimed in claim 1 energy-saving ultra-large methane synthesizing method producing different grades steam, is characterized in that the temperature that described first gas mixture enters the first methanol reactor in parallel after heating up is 210 DEG C ~ 230 DEG C.

The 11. energy-saving ultra-large methane synthesizing methods producing different grades steam as claimed in claim 1, is characterized in that each component content of described first gas mixture after heating up is H ₂be 40 ~ 70mol%; CO is 5 ~ 25mol%; CO ₂be 1 ~ 10mol%.

The 12. energy-saving ultra-large methane synthesizing methods producing different grades steam as claimed in claim 1, is characterized in that described first methanol reactor uses boiled water to remove methanol-fueled CLC reaction liberated heat.

The 13. energy-saving ultra-large methane synthesizing methods producing different grades steam as claimed in claim 1, it is characterized in that described first methanol reactor sends the first liquid-vapor mixture, after described first liquid-vapor mixture carries out vapor-liquid separation, produce the middle pressure steam that a pressure is 2.2MPag ~ 2.7MPag.

The 14. energy-saving ultra-large methane synthesizing methods producing different grades steam as claimed in claim 1, is characterized in that the temperature of the synthetic gas that described reaction formation unreacted is complete and methanol steam mixture is 240 DEG C ~ 260 DEG C.

The 15. energy-saving ultra-large methane synthesizing methods producing different grades steam as claimed in claim 1, is characterized in that the synthetic gas that described unreacted is complete and the temperature of methanol steam mixture after cooling are 210 DEG C ~ 220 DEG C.

The 16. energy-saving ultra-large methane synthesizing methods producing different grades steam as claimed in claim 1, is characterized in that the synthetic gas that described unreacted is complete and methanol steam mixture and described first gas mixture carry out heat exchange.

The 17. energy-saving ultra-large methane synthesizing methods producing different grades steam as claimed in claim 1, after it is characterized in that the synthetic gas that described unreacted is complete and methanol steam mixture and described first gas mixture carry out heat exchange, again after intersegmental condensation separation portion of product, then enter the second methanol reactor after carrying out heat exchange with final product and proceed methanol-fueled CLC and be obtained by reacting final product.

The 18. energy-saving ultra-large methane synthesizing methods producing different grades steam as claimed in claim 1, is characterized in that the synthetic gas that described unreacted is complete and methanol steam mixture and described circulation gas carry out heat exchange.

The 19. energy-saving ultra-large methane synthesizing methods producing different grades steam as claimed in claim 1, is characterized in that the synthetic gas that described unreacted is complete and methanol steam mixture and described circulation gas carry out heat exchange.

The 20. energy-saving ultra-large methane synthesizing methods producing different grades steam as claimed in claim 1, is characterized in that described second methanol reactor uses boiled water to remove methanol-fueled CLC reaction liberated heat.

The 21. energy-saving ultra-large methane synthesizing methods producing different grades steam as claimed in claim 1, it is characterized in that described second methanol reactor sends the second liquid-vapor mixture, it is the low-pressure steam of 1.1MPag ~ 1.7MPag that described second liquid-vapor mixture carries out producing a pressure after carbonated drink is separated.

The 22. energy-saving ultra-large methane synthesizing methods producing as claimed in claim 1 different grades steam, it is characterized in that described final product through cooled temperature be 30 DEG C ~ 45 DEG C.

The 23. energy-saving ultra-large methane synthesizing methods producing different grades steam as claimed in claim 1, is characterized in that carrying out heat exchange with described first gas mixture in described final product process of cooling.

The 24. energy-saving ultra-large methane synthesizing methods producing different grades steam as claimed in claim 1, is characterized in that the alcohol net value in described final product is 18 ~ 21mol%.

25. 1 kinds of devices realizing the energy-saving ultra-large methane synthesizing method of the production different grades steam described in any one of claim 1 to 24 claim, is characterized in that, comprising:

First refrigerating unit, described first refrigerating unit has the first gas mixture entrance, the first mixed gas outlet, the first final product entrance, the first final product outlet, wherein said first gas mixture entrance connects one end of a virgin gas transfer lime and one end of the first circulation gas transfer lime, described virgin gas transfer lime sends virgin gas here, and described first circulation gas transfer lime sends circulation gas here;

Two the first methanol reactors, the top of each the first methanol reactor is configured with the second gas mixture entrance, top is configured with the first liquid-vapor mixture outlet, bottom is configured with the first Separation of Water refluxing opening, bottom is configured with the complete synthetic gas of the first unreacted and methanol steam mixture outlet, and wherein each second gas mixture entrance is connected with the first mixed gas outlet in described first refrigerating unit by one first mixed gas pipeline;

One first vapour liquid separator, described first vapour liquid separator is at least configured with two the first liquid-vapor mixture entrances, two the first Separation of Water outlets and a middle pressure steam outlet, wherein two the first liquid-vapor mixture entrances to export with first liquid-vapor mixture on a corresponding methanol reactor top respectively by two first liquid-vapor mixture transfer limes and connect, and two the first Separation of Waters outlets connect with the first Separation of Water refluxing opening of corresponding methanol reactor bottom respectively by two first Separation of Water transfer limes; Middle pressure steam is sent in described middle pressure steam outlet;

One second methanol reactor, the top of described second methanol reactor is configured with the complete synthetic gas of first unreacted and methanol steam mixture inlet and two the second liquid-vapor mixtures outlets, bottom is configured with one first final product outlet and two the second Separation of Water refluxing openings, and the complete synthetic gas of described first unreacted and methanol steam mixture inlet are connected by synthetic gas that the first unreacted the is complete synthetic gas complete with the first unreacted bottom two the first methanol reactors with methanol steam mixture transfer lime and methanol steam mixture outlet; Described first final product outlet is connected with the first final product entrance in described first refrigerating unit by the first final product transfer lime;

One second vapour liquid separator, described second vapour liquid separator is at least configured with two the second liquid-vapor mixture entrances, two the second Separation of Water outlet and low-pressure steam outlet, wherein two the second liquid-vapor mixture entrances export respectively by the second liquid-vapor mixture that two second liquid-vapor mixture transfer limes are corresponding with described second methanol reactor and connect, two the second Separation of Water outlets connect respectively by the second Separation of Water refluxing opening that two second Separation of Water transfer limes are corresponding with described second methanol reactor, and described low-pressure steam outlet sends low-pressure steam;

Second refrigerating unit, described second refrigerating unit has the second final product entrance and the outlet of the second final product, and the second final product entrance is exported with the first final product in described first refrigerating unit by the second final product transfer lime and is connected;

3rd refrigerating unit, described 3rd refrigerating unit has the 3rd final product entrance and the outlet of the 3rd final product, and the 3rd final product entrance is exported with the second final product in described second refrigerating unit by the 3rd final product transfer lime and is connected;

One the 3rd gas-liquid separator, described 3rd gas-liquid separator has the 4th final product entrance, the first circulation gas outlet and separating liquid outlet, and wherein said 4th final product entrance is exported with the 3rd final product in described 3rd refrigerating unit by the 4th final product transfer lime and is connected; Described first circulation gas outlet connects one on the one hand and speeds to put pipe, is connected on the other hand by a recycle compressor with the other end of described first circulation gas transfer lime;

One reduced-pressure flash tank, described reduced-pressure flash tank has a separating liquid entrance, crude carbinol outlet and flashed vapour outlet, described separating liquid entrance is exported with the separating liquid on described 3rd gas-liquid separator by separating liquid transfer lime and is connected, described crude carbinol outlet exports crude carbinol, and flashed vapour is sent in described flashed vapour outlet.

26. devices as claimed in claim 25, it is characterized in that, described first refrigerating unit is gas-gas heat exchanger, and the second refrigerating unit is air cooler, and the 3rd refrigerating unit is water cooling heat exchanger.

27. devices as claimed in claim 25, it is characterized in that, also comprise the 4th refrigerating unit, described 4th refrigerating unit has the complete synthetic gas of the second unreacted and methanol steam mixture inlet, the synthetic gas that second unreacted is complete and methanol steam mixture outlet, 3rd gas mixture entrance or the second circulation gas entrance, 3rd mixed gas outlet or the outlet of the second circulation gas, the complete synthetic gas of described second unreacted and methanol steam mixture inlet are connected by synthetic gas that described second unreacted the is complete synthetic gas complete with the first unreacted bottom two the first methanol reactors with methanol steam mixture transfer lime and methanol steam mixture outlet, the complete synthetic gas of described second unreacted and methanol steam mixture outlet are connected by synthetic gas that the 3rd unreacted the is complete synthetic gas complete with the first unreacted of described second methanol reactor with methanol steam mixture transfer lime and methanol steam mixture inlet, described 3rd gas mixture entrance is connected with the first mixed gas outlet in described first refrigerating unit by the second mixed gas pipeline or the second circulation gas entrance is connected with described first circulation gas transfer lime by the second circulation gas transfer lime, described 3rd mixed gas outlet is connected with the second gas mixture entrance in two the first methanol reactors by the 3rd mixed gas pipeline or described second circulation gas exports to be connected by the 3rd circulation gas transfer lime with the second gas mixture entrance in two the first methanol reactors and to pass through the 3rd mixed gas pipeline and is connected with the second gas mixture entrance in two the first methanol reactors.

28. devices as described in claim 25 or 27, is characterized in that, a compressor of connecting in described virgin gas transfer lime.

29. devices as described in claim 25 or 27, it is characterized in that, described first methanol reactor is water-cooled methanol reactor.

30. devices as claimed in claim 29, it is characterized in that, some first reaction tubess are configured with in described water-cooled methanol reactor, copper-based catalysts is configured with in described first reaction tubes, described first gas mixture enters in described first reaction tubes, methanol-fueled CLC reaction occurs under the copper-based catalysts katalysis in described first reaction tubes, and described first reaction tubes is outer to be cooled by boiled water.

31. devices as claimed in claim 30, is characterized in that, described second methanol reactor is the board-like synthetic tower of IMC isothermal catalyzer being loaded on the isothermal fixed-bed reactor between heat transfer tube or being loaded on by catalyzer outside plank that CN203227477U describes.

32. devices as claimed in claim 31, is characterized in that, the reactant gases in described second methanol reactor flows to as axis or radial form.

33. devices as claimed in claim 31, it is characterized in that, the copper-based catalysts in described first methanol reactor is identical with the copper-based catalysts in the second methanol reactor, is high/low temperature active copper catalyst based.

34. devices as claimed in claim 31, it is characterized in that, the copper-based catalysts in described first methanol reactor is high temperature active copper-based catalysts, and the copper-based catalysts in described second methanol reactor is low temperature active copper-based catalysts.

35. devices as described in claim 24 or 27, it is characterized in that, in a preferred embodiment of the invention, described first refrigerating unit, the 4th refrigerating unit are gas-gas heat exchanger, and the second refrigerating unit is air cooler, and the 3rd refrigerating unit is water cooling heat exchanger.

36. 1 kinds of devices realizing the energy-saving ultra-large methane synthesizing method of the production different grades steam described in any one of claim 1 to 24 claim, is characterized in that, comprising:

5th refrigerating unit, described 5th refrigerating unit has the complete synthetic gas of the complete synthetic gas of the 4th gas mixture entrance, the 4th mixed gas outlet, the 3rd unreacted and methanol steam mixture inlet, the 3rd unreacted and methanol steam mixture outlet, wherein said 4th gas mixture entrance connects one end of a virgin gas transfer lime and one end of the first circulation gas transfer lime, described virgin gas transfer lime sends virgin gas here, and described first circulation gas transfer lime sends circulation gas here;

Two the first methanol reactors, the top of each the first methanol reactor is configured with the second gas mixture entrance, top is configured with the first liquid-vapor mixture outlet, bottom is configured with the first Separation of Water refluxing opening, bottom is configured with the complete synthetic gas of the first unreacted and methanol steam mixture outlet, and wherein each second gas mixture entrance is connected with the 3rd mixed gas outlet in described 5th refrigerating unit by one first mixed gas pipeline; The complete synthetic gas of the first unreacted bottom two the first methanol reactors is connected by the synthetic gas that the 4th unreacted the is complete synthetic gas complete with the 3rd unreacted of described 5th refrigerating unit with methanol steam mixture transfer lime and methanol steam mixture inlet with methanol steam mixture outlet and after connecing;

One first vapour liquid separator, described first vapour liquid separator is at least configured with two the first liquid-vapor mixture entrances, two the first Separation of Water outlets and a middle pressure steam outlet, wherein two the first liquid-vapor mixture entrances to export with first liquid-vapor mixture on a corresponding methanol reactor top respectively by two first liquid-vapor mixture transfer limes and connect, and two the first Separation of Waters outlets connect with the first Separation of Water refluxing opening of corresponding methanol reactor bottom respectively by two first Separation of Water transfer limes; Middle pressure steam is sent in described middle pressure steam outlet;

6th refrigerating unit, described 6th refrigerating unit has the complete synthetic gas of the complete synthetic gas of the 4th unreacted and methanol steam mixture inlet, the 4th unreacted and methanol steam mixture outlet, and the complete synthetic gas of the 4th unreacted of described 6th refrigerating unit and methanol steam mixture inlet are connected by synthetic gas that the 5th unreacted the is complete synthetic gas complete with the 3rd unreacted of described 5th refrigerating unit with methanol steam mixture transfer lime and methanol steam mixture outlet;

4th gas-liquid separation device, described 4th gas-liquid separation device has the complete synthetic gas of the 5th unreacted and the outlet of methanol steam mixture inlet, the complete syngas outlet of the first unreacted and the first separating liquid, and the complete synthetic gas of the 5th unreacted of described 4th gas-liquid separation device and methanol steam mixture inlet are connected by synthetic gas that the 6th unreacted the is complete synthetic gas complete with the 4th unreacted of described 6th refrigerating unit with methanol steam mixture transfer lime and methanol steam mixture outlet;

One second methanol reactor, the top of described second methanol reactor is configured with the complete synthetic gas entrance of first unreacted and two the second liquid-vapor mixtures outlets, and bottom is configured with one first final product outlet and two the second Separation of Water refluxing openings;

One second vapour liquid separator, described second vapour liquid separator is at least configured with two the second liquid-vapor mixture entrances, two the second Separation of Water outlet and low-pressure steam outlet, wherein two the second liquid-vapor mixture entrances export respectively by the second liquid-vapor mixture that two second liquid-vapor mixture transfer limes are corresponding with described second methanol reactor and connect, two the second Separation of Water outlets connect respectively by the second Separation of Water refluxing opening that two second Separation of Water transfer limes are corresponding with described second methanol reactor, and described low-pressure steam outlet sends low-pressure steam;

7th refrigerating unit, described 7th refrigerating unit has the 5th final product entrance, the 5th final product outlet, the second unreacted complete synthetic gas entrance, the complete syngas outlet of the second unreacted, 5th final product entrance of described 7th refrigerating unit is exported with the first final product bottom described second methanol reactor by the 5th final product transfer lime and is connected, and the second unreacted complete synthetic gas entrance of described 7th refrigerating unit is connected with the complete syngas outlet of the first unreacted of described 4th gas-liquid separation device by the first unreacted complete synthetic gas transfer lime; The complete syngas outlet of second unreacted of described 7th refrigerating unit is connected by the synthetic gas entrance that the second unreacted complete synthetic gas transfer lime is complete with first unreacted at described second methanol reactor top;

Second refrigerating unit, described second refrigerating unit has the second final product entrance and the outlet of the second final product, and the second final product entrance is exported with the 5th final product in described 7th refrigerating unit by the 6th final product transfer lime and is connected;

3rd refrigerating unit, described 3rd refrigerating unit has the 3rd final product entrance and the outlet of the 3rd final product, and the 3rd final product entrance is exported with the second final product in described second refrigerating unit by the 7th final product transfer lime and is connected;

One the 3rd gas-liquid separator, described 3rd gas-liquid separator has the 4th final product entrance, the first circulation gas outlet and the outlet of the second separating liquid, and wherein said 4th final product entrance is exported with the 3rd final product in described 3rd refrigerating unit by the 8th final product transfer lime and is connected; Described first circulation gas outlet connects one on the one hand and speeds to put pipe, is connected on the other hand by a recycle compressor with the other end of described first circulation gas transfer lime;

One reduced-pressure flash tank, described reduced-pressure flash tank has one the 3rd separating liquid entrance, crude carbinol outlet and flashed vapour outlet, described 3rd separating liquid entrance is exported with the second separating liquid on described 3rd gas-liquid separator by the first separating liquid transfer lime and is connected, described crude carbinol outlet exports crude carbinol, and flashed vapour is sent in described flashed vapour outlet;

8th refrigerating unit, described 8th refrigerating unit has the 4th separating liquid entrance, the 4th separating liquid outlet, described 4th separating liquid entrance is exported with the first separating liquid of described 4th gas-liquid separation device by the second separating liquid transfer lime and is connected, and the 4th separating liquid outlet of described 8th refrigerating unit is connected with described first separating liquid transfer lime by the 3rd separating liquid transfer lime.

37. devices as claimed in claim 36, is characterized in that, a compressor of connecting in described virgin gas transfer lime.

38. devices as claimed in claim 36, it is characterized in that, described first methanol reactor is water-cooled methanol reactor.

39. devices as claimed in claim 38, it is characterized in that, some first reaction tubess are configured with in described water-cooled methanol reactor, copper-based catalysts is configured with in described first reaction tubes, described first gas mixture enters in described first reaction tubes, methanol-fueled CLC reaction occurs under the copper-based catalysts katalysis in described first reaction tubes, and described first reaction tubes is outer to be cooled by boiled water.

40. devices as claimed in claim 39, is characterized in that, described second methanol reactor is the board-like synthetic tower of IMC isothermal catalyzer being loaded on the isothermal fixed-bed reactor between heat transfer tube or being loaded on by catalyzer outside plank that CN203227477U describes.

41. devices as claimed in claim 40, is characterized in that, the reactant gases in described second methanol reactor flows to as axis or radial form.

42. devices as claimed in claim 40, it is characterized in that, the copper-based catalysts in described first methanol reactor is identical with the copper-based catalysts in the second methanol reactor, is high/low temperature active copper catalyst based.

43. devices as claimed in claim 40, it is characterized in that, the copper-based catalysts in described first methanol reactor is high temperature active copper-based catalysts, and the copper-based catalysts in described second methanol reactor is low temperature active copper-based catalysts.

44. devices as claimed in claim 36, it is characterized in that, described second refrigerating unit is air cooler, 3rd refrigerating unit is water cooling heat exchanger, 5th refrigerating unit is gas-gas heat exchanger, the 6th refrigerating unit is air cooler, 7th refrigerating unit is gas-gas heat exchanger, and the 8th refrigerating unit is water cooling heat exchanger.