CN114621053A - Can reduce CO2Method for preparing methanol from landfill gas by discharging and improving energy efficiency - Google Patents
Can reduce CO2Method for preparing methanol from landfill gas by discharging and improving energy efficiency Download PDFInfo
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Abstract
The invention discloses a method for reducing CO2A method for producing methanol from landfill gas with improved energy efficiency. Regulating landfill gas and water vapor to a proper proportion, mixing, preparing hydrogen-poor synthesis gas in a reforming reactor, and electrolyzing water by using renewable energy to prepare green H2Adjusting the hydrogen-carbon ratio in the synthesis gas to the optimum hydrogen-carbon ratio [ H2/(2CO+3CO2)＝0.9‑1.1]Directly sending the mixture to a methanol reactor to synthesize methanol. The invention effectively improves the energy efficiency and CO in the process of preparing the methanol from the landfill gas by comprehensively utilizing the tail gas circulation and the internal energy of the process system2Equivalent emission reduction rate. The treatment capacity of the landfill gas is 4577.29m3The energy efficiency of the whole process of preparing the methanol from the landfill gas is 88.50 percent under the working condition of 0.95 of recycle ratio and CO2The equivalent emission reduction rate is 95.32%. The invention discloses a new process for preparing methanol from landfill gas,not only can reduce CO2And CH4Isothermal chamber gas discharge and high value-added product methanol production are realized, and the method is an effective technical path for realizing the aims of carbon peak reaching and carbon neutralization.
Description
The technical field is as follows:
the invention relates to a method for preparing landfill gas by reforming landfill gasThe obtained synthesis gas is used for synthesizing methanol and simultaneously realizing CO2A methanol synthesis process that minimizes emissions and maximizes energy efficiency.
Background art:
billions of tons of municipal waste are produced in every year all over the world at present, and most of the waste is directly buried without any treatment. The municipal landfill volume in china has increased dramatically from 3.65 million tons in 2013 to 5.84 million tons in 2019, which brings about various environmental problems related to landfill gas. Landfill gas is a gas mixture obtained by anaerobic biodegradation of refuse in a landfill. The landfill gas comprises a greenhouse gas CH4(50-60 mol%) and CO2(40-50 mol%) and, in addition, a small proportion of N2，O2，H2S and volatile organic compounds. If the landfill gas is directly discharged into the atmosphere without any treatment, not only a large amount of greenhouse gas emission is caused, but also CH4Are flammable gases and may present safety issues, and therefore it is necessary to enhance the collection and utilization of landfill gas. At present, most of the landfill gas is used as fuel for heating or generating electricity, and the way really realizes the reutilization of the landfill gas. However, it is not negligible that a large amount of CO is generated regardless of heating or power generation2This is not conducive to slowing down the greenhouse effect. CO in the landfill gas2And CH4Reforming to synthesis gas, from which methanol synthesis is a promising option. The method reduces CO2Discharging and simultaneously obtaining methanol with high added value.
Methanol is an important platform chemical, and can be used for producing various high-value-added chemicals such as acetic acid, formaldehyde, low-carbon olefin and the like by taking the methanol as a raw material. Meanwhile, the methanol can be used as a fuel cell or mixed with gasoline. At present, most of methanol is produced by using natural gas as a carbon source, so the price of the methanol is greatly influenced by the price of the natural gas. The process for preparing the methanol by using the landfill gas can solve the problem. However, the direct use of landfill gas for methanol production still facesCertain challenge, the hydrogen-carbon ratio of the synthesis gas obtained by reforming the landfill gas often cannot reach the optimal hydrogen-carbon ratio [ H ] required by methanol synthesis2/(2*CO+3CO2)＝0.9-1.1]Therefore, in order to adjust the hydrogen-carbon ratio, the invention proposes a method for adjusting the hydrogen-carbon ratio by supplementing extra H2Process route for adjusting the hydrogen-to-carbon ratio to produce methanol, in which H2Is prepared by electrolyzing water by renewable energy sources. The invention realizes the CO of the process flow for preparing the methanol from the landfill gas by comprehensively utilizing the tail gas circulation and the internal energy of the process2Emissions are minimized and energy efficiency is maximized.
The reactions involved in the reforming reactor are as follows:
the reactions involved in the methanol reactor are as follows:
the invention content is as follows:
the invention aims to provide a novel process for preparing methanol from landfill gas, so that the landfill gas can be effectively returnedAnd (4) recycling. The energy efficiency and CO of the process for preparing the methanol from the landfill gas are improved by comprehensively utilizing the tail gas circulation and the internal energy of the process2The emission reduction rate is effectively improved.
In order to achieve the above purpose, the invention adopts the following technical scheme: a method for preparing methanol from landfill gas comprises the following steps:
the first step is as follows: preparing hydrogen-deficient synthesis gas from landfill and steam through a reforming reaction in a reforming reactor filled with a reforming catalyst;
the second step is that: the synthesis gas is adjusted and compared by adding hydrogen, and then methanol is prepared by methanol synthesis reaction in a methanol reactor filled with a methanol synthesis catalyst;
the third step: methanol is separated from the unreacted synthesis gas, one part of the unreacted synthesis gas is recycled to the methanol reactor, and the other part of the unreacted synthesis gas is taken as purge gas and is sent to a combustor after being mixed with additional natural gas and air.
Preferably, the operating temperature of the reforming reactor in the first step is 700-900 ℃; the operation pressure of the reforming reactor is 0.3-0.7 MPa; CH (CH)4/CO2/H2The molar ratio of O is 1 (0.5-0.9) to 1-1.5.
Preferably, the amount of hydrogen added in the second step is such as to adjust the hydrogen-to-carbon molar ratio [ H ] of the synthesis gas2/(2CO+3CO2)]Is 0.9-1.1.
Preferably, the operating temperature of the methanol reactor in the third step is 230-280 ℃ and the operating pressure is 4-6 MPa.
It is preferable that the recycle ratio of the unreacted gas in the third step is 0.6 to 0.95 (recycle ratio: recycled unreacted gas/total unreacted gas).
Preferably, the high temperature hydrogen-depleted synthesis gas in the first step contains water vapor, and is condensed to 10-20 ℃ to remove water in the first flash tank. Preferably, the high temperature hydrogen-depleted synthesis gas undergoes at least two heat exchanges during condensation.
Preferably, the high-temperature hydrogen-lean synthesis gas at the outlet of the reforming reactor and the mixed gas at the inlet of the reforming reactor exchange heat in a first heat exchanger, wherein the first heat exchanger is positioned at the downstream of the reforming reactor and at the upstream of the second heater. And exchanging heat between the high-temperature lean hydrogen synthesis gas obtained in the reforming reactor and the first process water in a second heat exchanger, and sending the heated process water to a steam drum. Wherein the second heat exchanger is located downstream of the first heat exchanger and upstream of the first cooler.
Preferably, the high temperature outlet gas of the methanol reactor in the second step needs to be condensed to 10-20 ℃, and the separation of the unreacted gas and methanol is realized in the second flash tank. Preferably, the high-temperature gas at the outlet of the methanol reactor is subjected to at least two-stage heat exchange in the condensation process.
Preferably, the high-temperature gas at the outlet of the methanol reactor and the mixed gas entering the reactor exchange heat in a third heat exchanger, wherein the third heat exchanger is positioned at the downstream of the second mixer and at the upstream of the methanol reactor. Preferably, the high-temperature gas at the outlet of the methanol reactor exchanges heat with the process water in the fourth heat exchanger, and the heated process water is sent to the steam drum. Wherein the fourth heat exchanger is located downstream of the third heat exchanger and upstream of the second cooler.
Preferably, the purge gas, the air and the added natural gas are combusted in the combustor to obtain the high-temperature tail gas with the temperature of 900-1000 ℃. Preferably, the high-temperature tail gas is subjected to at least three-stage heat exchange in the temperature reduction process.
Preferably, the high-temperature tail gas and the mixed gas entering the reforming reactor exchange heat in a fifth heat exchanger. Wherein the fifth heat exchanger is located downstream of the first heat exchanger and upstream of the reforming reactor.
Preferably, the high-temperature tail gas provides heat for the reforming reactor through the sixth heat exchanger. Wherein the sixth heat exchanger is located downstream of the fifth heat exchanger and upstream of the reforming reactor.
Preferably, the high-temperature tail gas and the air exchange heat in a seventh heat exchanger. Wherein the seventh heat exchanger is located downstream of the sixth heat exchanger and upstream of the air feed gas.
Preferably, in the second step, the heat released by the methanol reaction exchanges heat with liquid water obtained by the separation of the steam drum in an eighth heat exchanger to obtain medium-pressure steam.
Preferably, the water vapor used as the reaction feed in the first step is derived from medium pressure steam provided by a steam drum.
Will be dumpsThe landfill gas is fed to a reforming reactor, and steam is supplied to the reforming reactor, and the landfill gas and the steam are reformed in the reforming reactor to obtain a hydrogen-depleted synthesis gas. And after the hydrogen-poor synthesis gas is cooled and condensed, carrying out flash evaporation to remove moisture to obtain the synthesis gas. By addition of H2Adjusting the hydrogen-carbon ratio in the synthetic gas to the optimal hydrogen-carbon ratio required by methanol synthesis, reacting the obtained synthetic gas in a methanol reactor to generate methanol, cooling and condensing unreacted gas and crude methanol, performing flash separation, circulating a part of the unreacted gas to the methanol reactor, taking the other part of the unreacted gas as purge gas, and sending the purge gas to a combustor. The invention provides a scheme for tail gas circulation and comprehensive utilization of internal energy of the process, which comprises the steps of preheating the high-temperature gas at the outlet of a reforming reactor to the feed gas, preheating the high-temperature gas at the outlet of a methanol reactor to the feed gas, and secondarily preheating the feed gas of the reforming reactor by using the high-temperature gas obtained at the outlet of a combustor until the temperature of the feed gas reaches 700-. And (3) respectively exchanging heat between the process water and the high-temperature gas at the outlet of the reforming reactor, the high-temperature gas at the outlet of the methanol reactor and the methanol reactor to finally obtain medium-pressure steam, wherein the medium-pressure steam can be used as a source of steam of reaction raw materials.
The invention discloses a method for synthesizing methanol by using synthesis gas obtained by reforming landfill gas and realizing CO2A methanol synthesis process that minimizes emissions and maximizes energy efficiency. Which comprises reforming landfill gas to produce synthetic gas (CH)4And CO2Combined reforming), by addition of H2To adjust the hydrogen-carbon ratio in the synthesis gas to the optimal hydrogen-carbon ratio [ H ] needed for synthesizing methanol2/(2CO+3CO2)＝0.9-1.1]The unreacted gas is partly recycled and partly used as purge gas and sent to the burner. The invention provides a scheme for tail gas circulation and comprehensive utilization of internal energy of the process. Preheating the high-temperature gas at the outlet of the reforming reactor with the feed gas, preheating the high-temperature gas at the outlet of the methanol reactor with the feed gas, and secondarily preheating the feed gas of the reforming reactor by using the high-temperature gas obtained at the outlet of the combustor until the temperature of the feed gas reaches 700-. The process water is respectively connected with the outlet of the reforming reactorAnd (3) exchanging heat between the warm gas, the high-temperature gas at the outlet of the methanol reactor and the methanol reactor to finally obtain medium-pressure steam, wherein the medium-pressure steam can be used as a source of water vapor of reaction raw materials. The energy efficiency of the landfill gas process reaches 88.50 percent and CO is comprehensively utilized through tail gas circulation and the internal energy of the process2The equivalent emission reduction rate reaches 95.32 percent. The invention has the beneficial effects that the landfill gas is changed into valuable, and the waste is converted into clean fuel with high added value. The invention provides a scheme for tail gas circulation and comprehensive utilization of process internal energy, and effectively improves the energy efficiency and CO in the process of preparing methanol from landfill gas2And (4) the emission reduction rate.
This method will be described in more detail below.
Preparing synthesis gas:
controlling the pressure of the landfill gas to be 0.5-0.7MPa, and controlling the landfill gas to be 101]Has CH as the main component4、CO2、N2And O2. 250 ℃ and 280 ℃ of water vapor (102) with the pressure of 0.5-0.7MPa]With landfill gas [101 ]]Mixing, controlling CH4/CO2/H2The molar ratio of O is 1 (0.5-0.9) to 1-1.5, the landfill gas [101 ]]And water vapor [102 ]]Mixing in a mixer M101, mixing the gas [103 ]]Preheating by heat exchangers E101 and E102 to obtain a feed gas [105 ] of 0.5-0.7MPa and 700-]Feeding gas [105 ]]And (2) introducing the mixture into a reforming reactor R101, controlling the operating temperature of the reforming reactor R101 to be 700-900 ℃ and the operating pressure to be 0.5-0.7MPa, and simultaneously carrying out steam reforming, water-gas shift reaction and dry reforming of methane in the reforming reactor R101, wherein the reaction equations are shown as (1), (2) and (3). High-temperature hydrogen-poor synthesis gas [106 ] is obtained at the outlet of the reforming reactor R101]. High temperature lean hydrogen syngas [106]The mixed gas [103 ] is preheated in a heat exchanger E101]Then obtaining the low-temperature hydrogen-poor synthesis gas [107]]. But low temperature lean hydrogen synthesis gas [107]]Still containing a large amount of water vapor, and low-temperature synthesis gas [107]]After further condensation by the heat exchanger E103 and the condenser E104, the temperature is reduced to 10-20 ℃, flash separation is carried out in the flash tank V101, and liquid water flows out from the lower end of the flash tank V101 under the action of gravity. Synthesis gas [111]Then fromAnd the upper end of the flash tank V101 is discharged. Obtaining green hydrogen (113) with pressure of 0.7-1MPa by electrolyzing water through renewable energy]Compressing the gas by a compressor C102 at 4-6MPa to obtain a hydrogen-deficient synthetic gas [112 ]]Compressed hydrogen [114]]And unreacted gas [125 ] recycled back]Mixing in a mixer M102 to obtain a synthesis gas [115]By regulating hydrogen gas [113 ]]In an amount such that synthesis gas [115]]To the optimum hydrogen-to-carbon ratio [ H ] required for methanol synthesis2/(2*CO+3CO2)＝0.9-1.1]。
Preparing methanol:
the obtained mixed gas [115] is heated by a heat exchanger E105 and a heater E106 to obtain the synthesis gas [117] with the temperature of 230 ℃ and 280 ℃. The synthesis gas [117] is used for synthesizing methanol in a methanol reactor R102, the catalyst is a modified copper-based catalyst in the methanol reactor R102, the reaction temperature is 230-280 ℃ and the reaction pressure is 4-6MPa, the high-temperature gas at the outlet of the methanol reactor is condensed to 10-20 ℃ through a heat exchanger E107 and a condenser E108, flash separation is carried out in a flash evaporation tank V102, and the crude methanol [122] containing water flows out from the bottom. Unreacted gas [123] is withdrawn from the top of flash tank V102 and split via splitter F101, and a proportion of unreacted gas [114] is recycled to methanol reactor R102, the recycle ratio being 0.6-0.95. The recycled unreacted gas [114] needs to be compressed to 4-6MPa by a compressor C103, and the gas [126] which is not recycled
As purge gas, it is sent to the burner R103 to be burned.
Tail gas circulation and comprehensive utilization of process internal energy:
the additional natural gas [137] and the purge gas [126] are mixed in a mixer M103 and then passed to a BURNER BURNER. The first process water [135] is pressurized to 4-5MPa through a pump P101, the process water [136] obtained by pressurization exchanges heat with the high-temperature outlet gas [107] of the reforming reactor in a heat exchanger E103, and the obtained process water [139] with the temperature of 170 and 270 ℃ is sent to a steam drum D101. The second process water [138] is pressurized to 4-5MPa through a pump P102, the process water [139] obtained through pressurization exchanges heat with the high-temperature outlet gas [119] of the methanol reactor R102 in a heat exchanger E107, and the obtained process water [140] with the temperature of 170-270 ℃ is sent to a steam drum D101. And pressurizing the third process water [141] to 4-5MPa through a pump P103, and directly sending the pressurized process water [142] to a steam drum D101. After separation in the steam drum D101, medium pressure steam (147) is obtained from the top and can be used as raw material gas. The process water [143] is obtained at the bottom, a part of the process water [144] is discharged after passing through the flow divider F102, and the other part of the process water [145] is heated by the heater E111 and then recycled to the steam drum D101, wherein the heat required by heating is derived from the heat [148] released by the methanol reaction. In addition, the high temperature tail gas [133] also delivers preheated air [129] into the burner and preheated air [130] into the burner R103.
Description of the drawings:
FIG. 1 is a schematic diagram of a process for producing methanol from landfill gas; wherein, M101 — first mixer; r101-reforming reactor; v101-first flash tank; c101-first compressor; c102-a second compressor; m102-a second mixer; r102-methanol reactor; v102 — second flash tank; f101-a first splitter; c103-third compressor; m103 — third mixer; r103-a burner; d101-steam drum; p101-a first booster pump; p102 — second booster pump; p103-third booster pump; e101-a first heat exchanger; e103-a second heat exchanger; e105-a third heat exchanger; e107-a fourth heat exchanger; e102-a fifth heat exchanger; e109-a sixth heat exchanger; e110-a seventh heat exchanger; e111-an eighth heat exchanger; e104 — first cooler; e108 — second cooler; e106-first heater; 101-landfill gas; 102-water vapor; 113-green hydrogen; 129-air; 127-plus natural gas; 135-first process water; 138-second process water; 141-third process water; 122-crude methanol; 134-burner tail gas; 147-medium pressure steam;
FIG. 2 is a graph showing the effect of tail gas recycle and process internal energy integration on energy efficiency at different recycle ratios;
FIG. 3 reflects the comprehensive utilization of tail gas recycle and internal process energy for CO at different recycle ratios2Influence graph of equivalent emission reduction rate.
The specific implementation mode is as follows:
the following examples are for illustrative purposes only and are not meant to limit the present invention.
Example 1:
the method for preparing the methanol from the landfill gas with the recycle ratio of 0.6 comprises the following steps:
feeding landfill gas to a reforming reactor, and supplying steam to the reforming reactor to control CH4/CO2/H2The molar ratio of O is 1:0.5: 1.5. In the reforming reactor, landfill and steam are reformed to obtain a hydrogen-depleted synthesis gas. Wherein the operation temperature of the reforming reactor is 820 ℃ and the operation pressure is 0.6 MPa. The high temperature hydrogen-lean syngas is condensed to 18 ℃ and the moisture is removed by flashing to obtain syngas. Green H produced by electrolysis of water from renewable energy sources2The hydrogen to carbon ratio of the synthesis gas entering the methanol reactor was adjusted to 0.9. The obtained synthesis gas reacts in a methanol reactor to generate methanol, wherein the operating temperature of the methanol reactor is 270 ℃, and the operating pressure is 5.5 MPa. Unreacted CO and CO2And H2Flash separation is carried out with the crude methanol, 60 percent of unreacted gas is recycled to the methanol reactor, and 40 percent of unreacted gas is taken as purge gas which is sent to a burner. Preheating the high-temperature gas at the outlet of a reforming reactor with the feed gas, preheating the high-temperature gas at the outlet of a methanol reactor with the feed gas, and secondarily preheating the feed gas of the reforming reactor by using the 975 ℃ high-temperature gas obtained at the outlet of a burner until the temperature of the feed gas reaches 820 ℃. And (3) respectively exchanging heat between the process water and the high-temperature gas at the outlet of the reforming reactor, the high-temperature gas at the outlet of the methanol reactor and the methanol reactor to finally obtain medium-pressure steam, wherein the medium-pressure steam can be used as a source of steam of reaction raw materials. The results are shown in Table 1, where the methanol yield is 15.76 ton/hr, the energy efficiency is 73.24%, and the CO content is2The equivalent emission reduction rate was 91.56%.
TABLE 1 simulation results for methanol production from landfill gas with recycle ratio of 0.6
Example 2:
the method for preparing the methanol from the landfill gas with the recycle ratio of 0.7 comprises the following steps:
feeding landfill gas to a reforming reactor while reformingMake-up steam in the reactor, control CH4/CO2/H2The molar ratio of O is 1:0.6: 1.4. In the reforming reactor, the landfill and steam are reformed to obtain a hydrogen-depleted synthesis gas. Wherein the operation temperature of the reforming reactor is 800 ℃, and the operation pressure is 0.5 MPa. The high temperature hydrogen-lean syngas is condensed to 16 ℃ and the moisture is removed by flashing to obtain syngas. Green H produced by electrolysis of water from renewable energy sources2The hydrogen to carbon ratio of the synthesis gas entering the methanol reactor was adjusted to 0.94. The obtained synthesis gas reacts in a methanol reactor to generate methanol, wherein the operating temperature of the methanol reactor is 250 ℃, and the operating pressure is 5 MPa. Unreacted CO and CO are mixed2And H2Flash separation is carried out with the crude methanol, 70% of the unreacted gas is recycled to the methanol reactor, and 30% of the unreacted gas is taken as purge gas which is sent to the burner. Preheating the high-temperature gas at the outlet of a reforming reactor to obtain feed gas, preheating the high-temperature gas at the outlet of a methanol reactor to obtain feed gas, and secondarily preheating the feed gas of the reforming reactor by using the 950 ℃ high-temperature gas obtained at the outlet of a burner until the temperature of the feed gas reaches 800 ℃. And (3) respectively exchanging heat between the process water and the high-temperature gas at the outlet of the reforming reactor, the high-temperature gas at the outlet of the methanol reactor and the methanol reactor to finally obtain medium-pressure steam, wherein the medium-pressure steam can be used as a source of steam of reaction raw materials. The results are shown in Table 2, where the methanol yield is 17 ton/hr, the energy efficiency is 78.83%, and CO is2The equivalent emission reduction rate was 92.29%.
TABLE 2 simulation results for methanol production from landfill gas with recycle ratio of 0.7
Example 3:
the method for preparing the methanol from the landfill gas with the recycle ratio of 0.8 comprises the following steps:
feeding landfill gas to a reforming reactor, and supplying steam to the reforming reactor to control CH4/CO2/H2The molar ratio of O is 1:0.7: 1.3. In the reforming reactionIn the reactor, landfill and steam are reformed to obtain the hydrogen-deficient synthesis gas. Wherein the operation temperature of the reforming reactor is 700 ℃ and the operation pressure is 0.3 MPa. The high temperature hydrogen-depleted synthesis gas is condensed to 10 ℃ and the moisture is removed by flashing to obtain synthesis gas. Green H produced by electrolysis of water from renewable energy sources2The hydrogen to carbon ratio of the synthesis gas entering the methanol reactor was adjusted to 1.02. The obtained synthesis gas reacts in a methanol reactor to generate methanol, wherein the operating temperature of the methanol reactor is 230 ℃, and the operating pressure is 4 MPa. Unreacted CO and CO2And H2Flash separation is carried out with the crude methanol, 80% of unreacted gas is recycled to the methanol reactor, and 20% of unreacted gas is taken as purge gas which is sent to a burner. Preheating the high-temperature gas at the outlet of a reforming reactor with the feed gas, preheating the high-temperature gas at the outlet of a methanol reactor with the feed gas, and secondarily preheating the feed gas of the reforming reactor by using the high-temperature gas of 1000 ℃ obtained at the outlet of a burner until the temperature of the feed gas reaches 700 ℃. And (3) respectively exchanging heat between the process water and the high-temperature gas at the outlet of the reforming reactor, the high-temperature gas at the outlet of the methanol reactor and the methanol reactor to finally obtain medium-pressure steam, wherein the medium-pressure steam can be used as a source of steam of reaction raw materials. The specific results are shown in Table 3, with a methanol yield of 18.55 tons/h, an energy efficiency of 85.87%, and CO2The equivalent emission reduction rate was 93.21%.
TABLE 3 simulation results for landfill gas to methanol with recycle ratio of 0.8
Example 4:
the method for preparing the methanol from the landfill gas with the recycle ratio of 0.9 comprises the following steps:
feeding landfill gas to a reforming reactor, and supplying steam to the reforming reactor to control CH4/CO2/H2The molar ratio of O is 1:0.8: 1.2. In the reforming reactor, landfill and steam are reformed to obtain a hydrogen-depleted synthesis gas. Wherein the operating temperature of the reforming reactor900 ℃ and an operating pressure of 0.7 MPa. The high temperature hydrogen-lean synthesis gas is condensed to 20 ℃ and the moisture is removed by flashing to obtain synthesis gas. Green H produced by electrolysis of water from renewable energy sources2The hydrogen to carbon ratio of the synthesis gas entering the methanol reactor was adjusted to 1.06. The obtained synthesis gas reacts in a methanol reactor to generate methanol, wherein the operating temperature of the methanol reactor is 280 ℃, and the operating pressure is 6 MPa. Unreacted CO and CO are mixed2And H2Flash separation is carried out with the crude methanol, 90% of the unreacted gas is recycled to the methanol reactor, and 10% of the unreacted gas is taken as purge gas which is sent to the burner. Preheating the high-temperature gas at the outlet of a reforming reactor to obtain feed gas, preheating the high-temperature gas at the outlet of a methanol reactor to obtain feed gas, and secondarily preheating the feed gas of the reforming reactor by using the high-temperature gas at 900 ℃ obtained at the outlet of a burner until the temperature of the feed gas reaches 900 ℃. And (3) respectively exchanging heat between the process water and the high-temperature gas at the outlet of the reforming reactor, the high-temperature gas at the outlet of the methanol reactor and the methanol reactor to finally obtain medium-pressure steam, wherein the medium-pressure steam can be used as a source of steam of reaction raw materials. It is noted that the heat generated by the combustion of the purge gas is not sufficient to provide heat to the reforming reactor, and additional natural gas needs to be supplemented in the combustor. The specific results are shown in Table 4, with a methanol yield of 20.72 ton/h, an energy efficiency of 86.06%, and CO2The equivalent emission reduction rate is 93.29%.
TABLE 4 simulation results for methanol production from landfill gas with recycle ratio of 0.9
Example 5:
the method for preparing the methanol from the landfill gas with the recycle ratio of 0.95 comprises the following steps:
feeding landfill gas to a reforming reactor, and supplying steam to the reforming reactor to control CH4/CO2/H2The molar ratio of O is 1:0.9: 1. In the reforming reactor, landfill and steam are reformed to obtain a hydrogen-depleted synthesis gas. It is composed ofIn the process, the operating temperature of the reforming reactor was 750 ℃ and the operating pressure was 0.6 MPa. The high temperature hydrogen-lean syngas is condensed to 18 ℃ and the moisture is removed by flashing to obtain syngas. Green H produced by electrolysis of water from renewable energy sources2The hydrogen to carbon ratio of the synthesis gas entering the methanol reactor was adjusted to 1.1. The obtained synthesis gas reacts in a methanol reactor to generate methanol, wherein the operating temperature of the methanol reactor is 270 ℃, and the operating pressure is 5.5 MPa. Unreacted CO and CO are mixed2And H2Flash separation is carried out with the crude methanol, 95% of the unreacted gas is recycled to the methanol reactor, and 5% of the unreacted gas is taken as purge gas which is sent to the burner. Preheating the high-temperature gas at the outlet of the reforming reactor with the feed gas, preheating the high-temperature gas at the outlet of the methanol reactor with the feed gas, and secondarily preheating the feed gas of the reforming reactor by utilizing the 940 ℃ high-temperature gas obtained at the outlet of the burner until the temperature of the feed gas reaches 750 ℃. And (3) respectively exchanging heat between the process water and the high-temperature gas at the outlet of the reforming reactor, the high-temperature gas at the outlet of the methanol reactor and the methanol reactor to finally obtain medium-pressure steam, wherein the medium-pressure steam can be used as a source of steam of reaction raw materials. It is noted that the heat generated by the combustion of the purge gas is not sufficient to provide heat to the reforming reactor, and additional natural gas needs to be added to the combustor. The results are shown in Table 5, where the methanol yield is 22.40 ton/hr, the energy efficiency is 88.50%, and CO is2The equivalent emission reduction rate is 95.32%.
TABLE 5 simulation results for methanol from landfill gas with recycle ratio of 0.95
Comparative example 1:
the method for preparing the methanol from the landfill gas without replenishing the hydrogen and with the circulation ratio of 0.6 comprises the following steps:
feeding landfill gas to a reforming reactor, and simultaneously supplying steam to the reforming reactor to control CH4/CO2/H2The molar ratio of O is 1:0.5: 1.5. In the reforming reactor, landfill gas andand reforming the steam to obtain the hydrogen-poor synthesis gas. Wherein the operation temperature of the reforming reactor is 820 ℃ and the operation pressure is 0.6 MPa. The high temperature hydrogen-lean syngas is condensed to 18 ℃ and the moisture is removed by flashing to obtain syngas. The obtained synthesis gas reacts in a methanol reactor to generate methanol, wherein the operating temperature of the methanol reactor is 270 ℃, and the operating pressure is 5.5 MPa. Unreacted CO and CO are mixed2And H2Flash separation was performed with the crude methanol, 60% of the unreacted gas was recycled to the methanol reactor, and 40% of the unreacted gas was used as purge gas. The tail gas circulation and the comprehensive utilization of the energy in the process are not carried out any more, namely, the high-temperature outlet gas of the reforming reactor and the methanol reactor does not preheat the feed gas any more, the temperature is directly reduced and the gas is condensed, the heat generated in the condensation process and the reaction heat released by the methanol reactor are not utilized any more, and the purge gas is directly discharged and is not used as fuel for supplying heat to the system. The heat required by the heater and the reforming reactor is provided by the combustion of natural gas. The results are shown in Table 6, where the methanol yield is 11.15 ton/hr, the system energy efficiency is 37.93%, and CO is2The equivalent emission reduction rate is 69.30%.
TABLE 6 unsupplemented with H2Simulation result of methanol production from landfill gas with recycle ratio of 0.6
Comparative example 2:
the method for preparing the methanol from the landfill gas with the recycle ratio of 0.6 comprises the following steps:
feeding landfill gas to a reforming reactor, and supplying steam to the reforming reactor to control CH4/CO2/H2The molar ratio of O is 1:0.5: 1.5. In the reforming reactor, landfill and steam are reformed to obtain a hydrogen-depleted synthesis gas. Wherein the operation temperature of the reforming reactor is 820 ℃ and the operation pressure is 0.6 MPa. The high temperature hydrogen-lean syngas is condensed to 18 ℃ and the moisture is removed by flashing to obtain syngas. Green H produced by electrolysis of water from renewable energy sources2Regulating is madeThe hydrogen to carbon ratio of the synthesis gas entering the methanol reactor was 0.9. The obtained synthesis gas reacts in a methanol reactor to generate methanol, wherein the operating temperature of the methanol reactor is 270 ℃, and the operating pressure is 5.5 MPa. Unreacted CO and CO are mixed2And H2Flash separation was performed with the crude methanol, 60% of the unreacted gas was recycled to the methanol reactor, and 40% of the unreacted gas was used as purge gas. The tail gas circulation and the comprehensive utilization of the energy in the process are not carried out, namely, the high-temperature outlet gas of the reforming reactor and the methanol reactor is not preheated to feed gas and is directly cooled and condensed, the heat generated in the condensation process and the reaction heat released by the methanol reactor are not utilized, and the purge gas is directly discharged and is not used as fuel to supply heat for the system. The heat required by the heater and the reforming reactor is provided by the combustion of natural gas. The results are shown in Table 7, where the methanol yield is 15.76 ton/h, the energy efficiency is 53.05%, and the CO content is2The equivalent emission reduction rate is 73.87%.
TABLE 7 simulation results for landfill gas to methanol with recycle ratio of 0.6
Comparative example 3:
the method for preparing the methanol from the landfill gas with the recycle ratio of 0.7 comprises the following steps:
feeding landfill gas to a reforming reactor, and simultaneously supplying steam to the reforming reactor to control CH4/CO2/H2The molar ratio of O is 1:0.6: 1.4. In the reforming reactor, landfill and steam are reformed to obtain a hydrogen-depleted synthesis gas. Wherein the operation temperature of the reforming reactor is 800 ℃, and the operation pressure is 0.5 MPa. The high temperature hydrogen-lean syngas is condensed to 16 ℃ and the moisture is removed by flashing to obtain syngas. Green H produced by electrolysis of water from renewable energy sources2The hydrogen to carbon ratio of the synthesis gas entering the methanol reactor was adjusted to 0.94. The obtained synthesis gas reacts in a methanol reactor to generate methanol, wherein the operating temperature of the methanol reactor is 250 ℃, and the operating pressure is 5 MPa. Unreacted CO and CO are mixed2And H2Flash separation was performed with the crude methanol, and 70% of the unreacted gas was recycled to the methanol reactor, and 30% of the unreacted gas was used as purge gas. The tail gas circulation and the comprehensive utilization of the energy in the process are not carried out, namely, the high-temperature outlet gas of the reforming reactor and the methanol reactor is not preheated to feed gas and is directly cooled and condensed, the heat generated in the condensation process and the reaction heat released by the methanol reactor are not utilized, and the purge gas is directly discharged and is not used as fuel to supply heat for the system. The heat required by the heater and the reforming reactor is provided by the combustion of natural gas. The results are shown in Table 8, where the yield of methanol is 17 ton/hr, the energy efficiency is 56.62%, and CO is2The equivalent emission reduction rate was 75.05%.
TABLE 8 simulation results for landfill gas to methanol with recycle ratio of 0.7
Comparative example 4:
the method for preparing the methanol from the landfill gas with the recycle ratio of 0.8 comprises the following steps:
feeding landfill gas to a reforming reactor, and supplying steam to the reforming reactor to control CH4/CO2/H2The molar ratio of O is 1:0.7: 1.3. In the reforming reactor, landfill and steam are reformed to obtain a hydrogen-depleted synthesis gas. Wherein the operation temperature of the reforming reactor is 700 ℃ and the operation pressure is 0.3 MPa. The high temperature hydrogen-lean synthesis gas is condensed to 10 ℃ and the moisture is removed by flashing to obtain synthesis gas. Green H produced by electrolysis of water from renewable energy sources2The hydrogen to carbon ratio of the synthesis gas entering the methanol reactor was adjusted to 1.02. The obtained synthesis gas reacts in a methanol reactor to generate methanol, wherein the operating temperature of the methanol reactor is 230 ℃, and the operating pressure isIs 4 MPa. Unreacted CO and CO are mixed2And H2Flash separation is carried out with the crude methanol, 80% of the unreacted gas is recycled to the methanol reactor, and 20% of the unreacted gas is used as purge gas. The tail gas circulation and the comprehensive utilization of the energy in the process are not carried out, namely, the high-temperature outlet gas of the reforming reactor and the methanol reactor is not preheated to feed gas and is directly cooled and condensed, the heat generated in the condensation process and the reaction heat released by the methanol reactor are not utilized, and the purge gas is directly discharged and is not used as fuel to supply heat for the system. The heat required by the heater and the reforming reactor is provided by the combustion of natural gas. The results are shown in Table 9, where the yield of methanol is 18.55 ton/hr, the energy efficiency is 60.67%, and CO is2The equivalent weight reduction rate was 76.38%.
TABLE 9 simulation results for methanol from landfill gas with recycle ratio of 0.8
Comparative example 5:
the method for preparing the methanol from the landfill gas with the recycle ratio of 0.9 comprises the following steps:
feeding landfill gas to a reforming reactor, and supplying steam to the reforming reactor to control CH4/CO2/H2The molar ratio of O is 1:0.8: 1.2. In the reforming reactor, landfill and steam are reformed to obtain a hydrogen-depleted synthesis gas. Wherein the operation temperature of the reforming reactor is 900 ℃ and the operation pressure is 0.7 MPa. The high temperature hydrogen-lean synthesis gas is condensed to 20 ℃ and the moisture is removed by flashing to obtain synthesis gas. Green H produced by electrolysis of water from renewable energy sources2The hydrogen to carbon ratio of the synthesis gas entering the methanol reactor was adjusted to 1.06. The obtained synthesis gas reacts in a methanol reactor to generate methanol, wherein the operating temperature of the methanol reactor is 280 ℃, and the operating pressure is 6 MPa. Unreacted CO and CO2And H2Flash separating with crude methanol, recycling 90% of unreacted gas to methanol reactor, and taking 10% of unreacted gas as purgeAnd (4) qi. The tail gas circulation and the comprehensive utilization of the energy in the process are not carried out, namely, the high-temperature outlet gas of the reforming reactor and the methanol reactor is not preheated to feed gas and is directly cooled and condensed, the heat generated in the condensation process and the reaction heat released by the methanol reactor are not utilized, and the purge gas is directly discharged and is not used as fuel to supply heat for the system. The heat required by the heater and the reforming reactor is provided by the combustion of natural gas. The results are shown in Table 10, where the yield of methanol was 20.72 ton/hr, the energy efficiency was 65.02%, and CO was2The equivalent emission reduction rate was 77.80%.
TABLE 10 simulation results for methanol from landfill gas with recycle ratio of 0.9
Comparative example 6:
the method for preparing the methanol from the landfill gas with the recycle ratio of 0.95 comprises the following steps:
feeding landfill gas to the reforming reactor, and simultaneously supplementing water vapor to the reforming reactor to control CH4/CO2/H2The molar ratio of O is 1:0.9: 1. In the reforming reactor, landfill and steam are reformed to obtain a hydrogen-depleted synthesis gas. Wherein the operation temperature of the reforming reactor is 750 ℃, and the operation pressure is 0.6 MPa. The high temperature hydrogen-lean syngas is condensed to 18 ℃ and the moisture is removed by flashing to obtain syngas. Green H produced by electrolysis of water from renewable energy sources2The hydrogen to carbon ratio of the synthesis gas entering the methanol reactor was adjusted to 1.1. The obtained synthesis gas reacts in a methanol reactor to generate methanol, wherein the operating temperature of the methanol reactor is 270 ℃, and the operating pressure is 5.5 MPa. Unreacted CO and CO are mixed2And H2Flash separation with crude methanol was carried out, 95% of the unreacted gas was recycled to the methanol reactor, and 5% of the unreacted gas was used as purge gas. The tail gas circulation and the comprehensive utilization of the energy in the process are not carried out, namely, the high-temperature outlet gas of the reforming reactor and the methanol reactor is not preheated, the temperature is directly reduced and condensed, and in addition, the temperature is reducedThe heat generated in the condensation process and the reaction heat released by the methanol reactor are not used any more, and the purge gas is directly discharged and is not used as fuel to supply heat for the system. The heat required by the heater and the reforming reactor is provided by the combustion of natural gas. The results are shown in Table 11, where the yield of methanol was 22.40 ton/hr, the energy efficiency was 66.18%, and CO content was2The equivalent emission reduction rate is 78.23 percent
TABLE 11 simulation results for methanol from landfill gas with recycle ratio of 0.95
Industrial applicability
The methanol can be directly used as a fuel cell or mixed with gasoline for use, and can also be used as a raw material for producing various high-value-added chemicals, such as acetic acid, formaldehyde, low-carbon olefin and the like. The process route for preparing the methanol from the landfill gas designed by the invention changes the landfill gas into valuable and provides a new way for treating and utilizing the landfill gas. In addition, the CO in the process is comprehensively utilized by the system2The emission reduction rate is improved to 95.32 percent, and CO is greatly reduced2Is an effective technical path for achieving the goals of carbon peak reaching and carbon neutralization.
Claims (6)
1. A method for preparing methanol from landfill gas comprises the following steps:
the first step is as follows: preparing hydrogen-deficient synthesis gas from landfill gas and steam through reforming reaction in a reforming reactor filled with a reforming catalyst;
the second step is that: adding hydrogen for synthesis gas regulation, and preparing methanol by methanol synthesis reaction in a methanol reactor filled with a methanol synthesis catalyst;
the third step: methanol is separated from the unreacted synthesis gas, one part of the unreacted synthesis gas is recycled to the methanol reactor, and the other part of the unreacted synthesis gas is taken as purge gas and is sent to a combustor after being mixed with additional natural gas and air.
2. The method of claim 1, wherein: the operation temperature of the reforming reactor in the first step is 700-900 ℃; the operation pressure of the reforming reactor is 0.3-0.7 MPa; CH (CH)4/CO2/H2The molar ratio of O is 1 (0.5-0.9) to 1-1.5.
3. The method of claim 1, wherein: in the second step, the amount of hydrogen added is such as to adjust the hydrogen-to-carbon molar ratio [ H ] of the synthesis gas2/(2CO+3CO2)]Is 0.9-1.1.
4. The method of claim 1, wherein: the operation temperature of the methanol reactor in the third step is 230-280 ℃, and the operation pressure is 4-6 MPa.
5. The method of claim 1, wherein: the circulating ratio of the unreacted gas in the third step is 0.6 to 0.95.
6. The method of claim 1, wherein: the purge gas, air and additional natural gas are combusted in a combustor to obtain high-temperature tail gas with the temperature of 900-; the high temperature tail gas provides heat for the reforming reactor.
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| CN116768702A (en) * | 2023-03-30 | 2023-09-19 | 北京理工大学 | Method for preparing methanol by carbon dioxide hydrogenation |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130487A (en) * | 2006-08-23 | 2008-02-27 | 中国科学院工程热物理研究所 | Method for landfill of gas fluidification dimethyl ether fuel by garbage |
| CN102307835A (en) * | 2008-12-08 | 2012-01-04 | 现代重工业株式会社 | Methanol synthesis method using synthesis gas generated by a mixed reforming of natural gas and carbon dioxide |
| CN102924228A (en) * | 2012-11-28 | 2013-02-13 | 西南化工研究设计院有限公司 | Method for producing methanol from semi-coke furnace tail gas |
| CN103264989A (en) * | 2013-05-20 | 2013-08-28 | 西南化工研究设计院有限公司 | Technique for recycling purge gas of device used for synthesizing methyl alcohol by utilizing synthesis gas |
| US20170362147A1 (en) * | 2014-08-04 | 2017-12-21 | Korea Research Institute Of Chemical Technology | Method for producing high-efficiency methanol capable of reducing emission of carbon dioxide |
| CN111547678A (en) * | 2020-04-08 | 2020-08-18 | 华南农业大学 | Method and system for preparing methanol by full-component thermal catalysis of marsh gas |
-
2021
- 2021-06-29 CN CN202110730850.7A patent/CN114621053A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130487A (en) * | 2006-08-23 | 2008-02-27 | 中国科学院工程热物理研究所 | Method for landfill of gas fluidification dimethyl ether fuel by garbage |
| CN102307835A (en) * | 2008-12-08 | 2012-01-04 | 现代重工业株式会社 | Methanol synthesis method using synthesis gas generated by a mixed reforming of natural gas and carbon dioxide |
| CN102924228A (en) * | 2012-11-28 | 2013-02-13 | 西南化工研究设计院有限公司 | Method for producing methanol from semi-coke furnace tail gas |
| CN103264989A (en) * | 2013-05-20 | 2013-08-28 | 西南化工研究设计院有限公司 | Technique for recycling purge gas of device used for synthesizing methyl alcohol by utilizing synthesis gas |
| US20170362147A1 (en) * | 2014-08-04 | 2017-12-21 | Korea Research Institute Of Chemical Technology | Method for producing high-efficiency methanol capable of reducing emission of carbon dioxide |
| CN111547678A (en) * | 2020-04-08 | 2020-08-18 | 华南农业大学 | Method and system for preparing methanol by full-component thermal catalysis of marsh gas |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116768702A (en) * | 2023-03-30 | 2023-09-19 | 北京理工大学 | Method for preparing methanol by carbon dioxide hydrogenation |
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