CN101649233B - Isothermal methanation process and device for the preparation of synthetic natural gas - Google Patents
Isothermal methanation process and device for the preparation of synthetic natural gas Download PDFInfo
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- CN101649233B CN101649233B CN 200910054761 CN200910054761A CN101649233B CN 101649233 B CN101649233 B CN 101649233B CN 200910054761 CN200910054761 CN 200910054761 CN 200910054761 A CN200910054761 A CN 200910054761A CN 101649233 B CN101649233 B CN 101649233B
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Abstract
The invention discloses an isothermal methanation process for the preparation of synthetic natural gas. The process comprises methanation step, methanation heat recovery steam-making step and condensate treatment step. The purified synthesis gas is performed methanation step, wherein the methanation step adopts at least two-stage methanation, the first stage methanation adopts an adiabatic methanation reactor to perform methanation and the later methanation in each stage adopts an isothermal methanation reactor to perform methanation. The invention also discloses an isothermal methanation device used in the isothermal methanation process for the preparation of synthetic natural gas. The isothermal methanation process and the isothermal methanation device for the preparation of synthetic natural gas of the invention have the advantages of energy-saving, environmental friend and low investment.
Description
Technical field
The present invention relates to coal or biomass is the chemical field that raw material is produced synthetic natural gas (SNG); Relating in particular to coal (coal) or biomass (biomass) is that raw material is produced synthetic natural gas (substitute/synthetic natural gas; Isothermal methanation process SNG) and device (IsothermalMethanation Process and Plant, SIECC/IMP).
Background technology
The present present situation of China's energy structure is many coals, weak breath, oil starvation, and also is difficult to take on a new look later on.The utilization of coal is main directly to do fuel at present, and utilising efficiency is low; And coal discharges objectionable impuritiess such as a large amount of waste gas, waste residue, polluted air, waters and soil in combustion processes; Carbon---the coal that chemical industry is used all is through railway and ship transportation in addition, and carriage load is heavy, has occupied a large amount of transport resources; Therefore concentrate and build large-scale coal or the biomass-making methane gas device (single series 4,000,000 sides/sky SNG) of many covers; After the carbon raw material gasification, gas purifies (removing the poisonous impurity of methanation catalyst) through modified (adjustment gaseous constituent); Pass through methanation again, it is imperative to produce the high heating value cleaning synthetic natural gas SNG that meets China's natural gas pipe-line transportation standard.
With helping solving following problem after coal or the biomass-making methane gas:
1) helps alleviating the Stress that Rail Highway transports;
2) improve near the environment protection of manufacturing district life of urban resident environment and the city;
3) solve the requirement for clean fuel away from the industrial and mining enterprises of neutralizing gas;
4) stablize natural gas supply.
Sweet natural gas standard such as the table 1 of present stage State Standard of the People's Republic of China GB17820-1999:
Table 1
But be the methanation device that raw material is produced synthetic natural gas (SNG) with coal or biomass at present, a cover industrialized unit only arranged in operation abroad, domestic also do not have demonstration unit, half industrialized unit or industrialized unit to move.And shortcomings such as the methane gas that adopts external existing industrialized unit to make exists that carbon content height, hydrogen richness are high, calorific value is low, of poor quality, heat recovery efficiency difference and flow process complicacy; Do not meet the Sweet natural gas standard of State Standard of the People's Republic of China GB17820-1999, therefore existing methanation technology can not satisfy the domestic requirement that coal or biomass are produced synthetic natural gas (SNG) maximization plant construction.In view of this; IMP isothermal methanation process of the present invention and device (Isothermal Methanation Processand Plant); What be intended to independent development China produces the novel energy-saving environment-friendly methanation technology of synthetic natural gas (SNG) with coal or biomass, utilizes the various energy of China and energy-saving and emission-reduction to have special meaning to China's Economic development and coordination.
The reaction that the methanation of synthetic gas relates to is following:
Methanation reaction:
CO+3H
2←→CH
4+H
2O+ΔH
CO
2+4H
2←→CH
4+2H
2O+ΔH
The carbon monodixe conversion reaction:
CO+H
2O←→CO
2+H
2+ΔH
Above-mentioned reaction is carried out simultaneously.Can be found out that by above-mentioned reaction formula methanation reaction is a strong exothermal reaction, accelerated reaction under the high temperature helps the methane reaction balance and moves right under the low temperature.
Because methanation is the catalytic reaction process of hydrogen and carbon oxide gas (being called synthetic gas) reaction; Become the synthetic gas of producing SNG after the modified purification of gas that makes from coal or biomass; Contain very high-load oxycarbide and hydrogen, this gas reacts on catalyzer and generates methane, discharges great amount of heat; One-pass thermal insulation warming can reach 400～600 ℃, is very easy to cause the inactivation of catalyzer and reactor drum to damage.
The subject matter of methanation system synthetic natural gas (SNG) is the temperature rise of control catalyst.Some present methanation process, main difference is exactly to control the not the same of the method that adopts in temperature.The most frequently used method is the gas circulation method, i.e. recycle gas dilution synthetic gas, and reaction heat is absorbed as sensible heat by a large amount of process gas.
Also there is following problem at present in the methanation process:
1. existing methanation process is complicated, and methanator quantity is many, and heat-exchange equipment is many;
2. internal circulating load is big, and circulating consumption is high, and single cover maximizes difficult;
3. adopt high-temperature gas round-robin methanation process at present, recycle compressor manufactures and designs difficult, and operational conditions is harsh, and investment is big; And adopt cold air round-robin methanation process, higher-grade heat recuperation to reduce, and steam production reduces (saturated or overheated), and efficiency of utilization descends.
Summary of the invention
One of technical problem to be solved by this invention provides a kind of isothermal methanation process of producing synthetic natural gas; Its through to the methanator texture improvement, move hot mode improvement, shunting, cold shock and other means gas-circulating system improved; Adopt isothermal methanation reactor drum bound gas circulation technology; Through shunting, cold shock and other means gas-circulating system is improved, flow process is simple, resistance reduces, investment is low, by-product high-pressure steam amount big (saturated or overheated).
Two of technical problem to be solved by this invention provides the employed isothermal methanation device of producing synthetic natural gas of above-mentioned technology.
The isothermal methanation process of producing synthetic natural gas as first aspect present invention; Comprise methanation step, methanation heat recovery steam-making step and phlegma treatment step; Synthetic gas after the purification gets into the methanation step and carries out methanation, it is characterized in that said methanation step adopts the above methanation of secondary at least; Wherein first step methanation adopts the adiabatic methanation reactor drum to carry out methanation, and the subsequent stages methanation adopts the isothermal methanation reactor drum to carry out methanation.
Optimization methane step of the present invention is the secondary methanation.
The concrete steps of technology of the present invention are: the synthetic gas after the purification is through overprotection bed GB; The total sulfur content that smart desulfurization to methanation catalyst can allow also is preheating to synthetic gas active starting temperature 200-300 ℃ of methanation catalyst; Obtain fresh synthetic gas and get into the methanation step; The pressure of fresh synthetic gas is 2.5-6.0MPa; The fresh synthesis gas that gets into the methanation step is divided into two-way; One the tunnel account for the 20-40V% of fresh synthesis gas volume first part's fresh synthesis gas mix the back with circulation gas and get into the first adiabatic methanation reactor drum and carry out first step methanation to generate temperature be 400-650 ℃ first high-temperature gas, first high-temperature gas passes, first heat recovery system reclaims reaction heat and obtains the first methanation gas, the temperature of the first methanation gas equals the active starting temperature of methanation catalyst; The second section fresh synthesis gas that another road accounts for the 60-80V% of fresh synthesis gas volume mixes the back and gets into the isothermal methanation reactor drum and carry out second stage methanation to generate temperature be 250-350 ℃ of second high-temperature gas with the first methanation gas; Obtaining temperature behind second high-temperature gas passes, second heat recovery system recovery reaction heat is 100-300 ℃ of product gas; A product gas part is delivered to the first adiabatic methanation reactor drum as circulation gas through being pressurized to fresh synthesis gas pressure, and rest part is delivered to methanation heat recovery steam-making step.
In aforesaid method, protection bed GB is normal temperature protection bed or high temperature protection bed.
In aforesaid method; Control the temperature out of adiabatic methanation reactor drum through the tolerance of Control Circulation gas; Make 650-700 ℃ of the permission service temperature that it is lower than methanation catalyst, wherein the tolerance of circulation gas is 0.5-1.5 with the tolerance ratio of the product gas that gets into methanation heat recovery steam-making step.
In aforesaid method, the hot(test)-spot temperature of isothermal methanation reactor drum is carried out through flow and the drum pressure that control gets into the fresh synthesis gas of isothermal methanation reactor drum, and wherein hot(test)-spot temperature is 550-700 ℃, and drum pressure is 4.0-9.0MPa.
In aforesaid method, isothermal methanation reactor drum cold side adopts the boiler and the service pump pump circulation type of cooling to remove heat, and the middle pressure saturation steam of while by-product 4.0-9.0MPa.
In aforesaid method, the first adiabatic methanation reactor drum can be pressed superheated vapour among the by-product 4.0-9.0MPa.
In aforesaid method, in the said fresh synthesis gas: H
2/ CO 3.3～3.4V%, CO
21.5V%, CH
416.3V%, C2H4 (or C2H6 and C3H8) 0.2～0.6V%, N2/Ar0.2～0.6V%
In aforesaid method, circulation gas adopts recycle compressor or boosting jet pump to carry out supercharging.
In aforesaid method, the resistance drop of whole methanation step is less than 5bar.
In aforesaid method; Comprise that also one is arranged on the methanation purification step between methanation step and the methanation heat recovery steam-making step; The product gas of being come by the methanation step at first gets into the second adiabatic methanation reactor drum, and to carry out methanation refining, and the product gas after refining is sent into methanation heat recovery steam-making step.
The isothermal methanation device of producing synthetic natural gas as second aspect present invention; Comprise protection bed GB, methanation device, methanation heat recovery steam-making device and phlegma treatment unit; It is characterized in that said methanation device comprises one first adiabatic methanation reactor drum, isothermal methanation reactor drum, first HRU, second HRU, supercharging circulation device; The outlet of said protection bed is divided into the two-way pipeline; Wherein first via pipeline connects the inlet of the first adiabatic methanation reactor drum; The outlet of second pipeline and first HRU and connect after connect the inlet of isothermal methanation reactor drum; The outlet of adiabatic methanation reactor drum connects the inlet of first HRU, and the outlet of isothermal methanation reactor drum connects the inlet of second HRU, and the outlet of second HRU is divided into two-way; One the tunnel connects methanation heat recovery steam-making device, and another road connects the inlet of the first adiabatic methanation reactor drum through the supercharging circulation device.
In the isothermal methanation device of producing synthetic natural gas of the present invention; The cold side of said isothermal methanation reactor drum connects a boiler; Said boiler is through pump circulation between service pump and the isothermal methanation reactor drum, the middle pressure saturation steam of by-product 4.0-9.0MPa simultaneously.
The first via pipeline of the outlet of protection bed and first variable valve and second variable valve that the second road pipeline is provided with interlock are the throughput ratio of fresh synthesis gas in the adjustable first via pipeline and the second road pipeline through first variable valve and second variable valve.
Said supercharging circulation device is recycle compressor or boosting jet pump.
In the isothermal methanation device of producing synthetic natural gas of the present invention, also comprise a methanation refining plant, this methanation refining plant is arranged between said methanation device and the methanation heat recovery steam-making device.
This methanation refining plant comprises the second adiabatic methanation reactor drum, and the inlet of the second adiabatic methanation reactor drum connects a way outlet of second HRU, and outlet connects methanation heat recovery steam-making device.
The present invention is through discovering: temperature of reaction has the greatest impact to methanation reaction, though temperature of reaction is high, the byproduct steam pressure rating is high, and Btu utilization efficient is high.If but the circulation gas temperature is high, harsh to the operational conditions requirement of recycle compressor, power consumption is big; And temperature of reaction is high, and whole methanation device needs particular design, and is high to the catalyst tolerates heat request, and steam content is also had requirement.And in research process, find, suitably reduce circulating flow rate and improve getting into methanation device CO content, can improve temperature of reaction.But discover that the catalyzer nickel content is high more, use temperature is low more, and is more responsive to poisonous substance, so the methanation reaction temperature also should not be low excessively.The present invention is through discovering the high nickel content methanation catalyst when temperature is too low, carbonylation and low-temperature inactive easily, and when temperature is too high, easily the sintering inactivation with analyse the carbon reaction.
In addition; The present invention is through discovering, pressure also is an important index to methanation reaction, and high pressure helps methane and generates; But its effect does not reduce the favourable methane of temperature to be generated significantly; Find that simultaneously methanation pressure is limited by vapor pressure and front end workshop section resistance drop, and system pressure is influential to equipment size, single series maximum capacity, reduces pressure in addition and can reduce heating strength a little.In research process, find: device is maximized pressurize and saving is invested favourable; But it is unfavorable to save compressed total power consumption (total power consumption of oxygen compressor power consumption and synthesic gas compressor and methane gas compressor work loss-rate are); If pressure is high more, add that the high more metal dusting that takes place more easily of CO content corrodes, the CO dividing potential drop is high more; Carbonylation reaction also takes place under specific temperature conditions easily; Therefore take all factors into consideration from device maximization and save compressed total power consumption, vapor pressure should not be low excessively, and is also unsuitable too high.4.0MPa～6.5MPa carbon raw material vapor pressure is fit to.
Content and the water yield of generation of the present invention through discovering methane in the fresh synthesis gas has certain relation, and methane content is low in the synthetic gas, and CO content will be relatively high; The methanation thermal discharge is big; The generation water yield is big, but it is little to the influence of synthetic natural gas SNG quality product to generate the water yield, and methane content is high; Help reducing response intensity, prolong the work-ing life of catalyzer.
Based on above research, the present invention improves the temperature of circulation gas as far as possible under the prerequisite that the loop compression equipment design is made and operation allows, and to improve heat recovery efficiency, reduces the long-time running expense.The present invention adopts isothermal methanation, has avoided causing methane gas (SNG) compressor investment and power consumption significantly to increase, simultaneously can the by-product saturation steam, use as power steam through overheated back, and can effectively reduce internal circulating load, simplification flow process, raising heat recovery efficiency.
After adopting technique scheme, the present invention compared with prior art has following advantage:
1, to synthetic gas H
2/ CO is at 2.0～6.0 (common H
2/ CO about 3.3) scope endoadaptation ability is strong.
2, strong to CO2 content adaptive faculty in the synthetic gas, therefore can reduce purifying investment and working cost.
3, in the SNG product ethane and propane content all at 0～tens ppm, no olefines organism.
4, can guarantee that synthetic gas do not analyse carbon.
5, can guarantee that the metal dusting corrosion does not take place methanation equipment; Metal dusting etching problem when avoiding steam superheating simultaneously.
6, can guarantee that carbonylation reaction does not take place, the protection methanation catalyst.
7, the methanation process that adopts the present invention to propose can reach national quality of natural gas primary standard, and is refining in conjunction with methanation, can reach better synthetic natural gas quality.
8, adopt methanation process of the present invention and device, adiabatic catalyst guaranteed the life-span more than 2 years in the methanation loop, and life expectancy is more than 3 years; The isothermal methanation catalyzer guaranteed the life-span more than 3 years, and life expectancy is more than 4 years.
9, adopt technology of the present invention and device, can realize that single series produces the ability of 4,000,000 side's synthetic natural gas SNG daily.
10, adopt technology of the present invention and device, can realize adopting minimum methanation progression (for example secondary methanation) and the simplest methanator.The product methane gas satisfies national quality of natural gas standard GB 17820-1999 one class natural gas through super-dry, and directly gas distributing system is advanced in compression.
11, adopt the temperature rise of gas circulation control methanator, avoid catalyzer inactivation at high temperature; It is good to reclaim higher-grade heat energy, the saturated or superheated vapour of the more high pressure of by-product.Therefore the present invention is an energy-saving technique.
12, methanation process of the present invention and device ordinary production do not have the useless solid waste gas of waste liquid and efflux, and process condensate can be used as oiler feed or cooling water replenishment reuse after simple process; Adopt the present invention that coal is made clean methane gas (synthetic natural gas SNG), can reduce the pollutent of the direct burning and exhausting of coal, improve environment.Therefore the present invention is an environment-protective process.
13, adopt industrialized methanation SNG catalyzer.
14, adopting the protection bed further to remove influences the active poisonous substance of methanation catalyst in the purified gas, prolong the work-ing life of methanation catalyst.
The circulation gas of 15, methanation loop feature adopts injector to carry out the supercharging circulation, reduces the facility investment of loop compression.
16, the superheated vapour of by-product uses for the recycle compressor turbine nearby, avoids the investment and the loss of long distances.
17, methanation process of the present invention and device are fit to the methanation of the synthetic gas of multiple carbon raw material gasifying process production.
The present invention can be a raw material with carbonaceousmaterials such as coal or biomass; Be applicable to powdered coal pressuring gasified (like SHELL gasification, GSP gasification, E-GAS gasification etc.), water coal slurry pressure gasification (like GE gasification, polynary slurry gasification, the gasification of opposed type burner etc.) or fixed bed pressured gasification (like LURGI dry bottom bed gasification FBDBG, BGL gasification etc.) or fluidized-bed gasification (for example U-GAS gasification, the grey gather qi togetherization etc. that melts) or other gasifying process, the follow-up supporting methanation process of coal system synthetic oil off-gas, gas such as methanol synthetic discharged gas delayed.
Further specify the present invention below in conjunction with accompanying drawing and embodiment.
Description of drawings
Fig. 1 is the synoptic diagram of the process unit of the embodiment of the invention 1.
Fig. 2 is the synoptic diagram of the process unit of the embodiment of the invention 2.
Embodiment
For the technique effect that makes technical characterictic of the present invention and generation is easy to clear understanding,, further set forth the present invention below in conjunction with preferred implementation shown in the drawings.
Embodiment 1
Referring to Fig. 1, produce the isothermal methanation device of synthetic natural gas, comprise protection bed GB, methanation device 100, methanation heat recovery steam-making device and phlegma treatment unit 200.Its methanation device comprises one first adiabatic methanation reactor drum M1, isothermal methanation reactor drum M2, the first heat recovery system WH1, the second heat recovery system WH2, recycle compressor C1 or a boosting jet pump E1; Methanation heat recovery steam-making device comprises the 3rd heat recovery system WH3, knockout drum 1, recycle compressor C2, condensing surface CW, knockout drum 2, moisture eliminator 3, recycle compressor C3.
Raw gas is regulated (H through conversion
2-CO
2)/(CO+CO
2) be slightly larger than 3, get into the normal temperature or the high temperature protection bed GB of the isothermal methanation device of producing synthetic natural gas through the synthetic gas MUG after purifying.Synthetic gas MUG after the purification total sulfur content that smart desulfurization to methanation catalyst can allow in normal temperature or high temperature protection bed GB earlier obtains fresh synthetic gas; And synthetic gas is preheating to active starting temperature 200-300 ℃ of methanation catalyst, the pressure of fresh synthetic gas is 2.5-6.0MPa.The poisonous substance of the methanation catalyst that workshop section brings into before overprotection bed GB removes is like sulfide, muriate, arsenide etc., to prolong the work-ing life of methanation catalyst.
The fresh synthetic gas that is come out by the outlet of protection bed GB is divided into two-way; One the tunnel account for the 20-40V% of fresh synthesis gas volume first part's fresh synthesis gas 10 mix the back with circulation gas 20 and get into the first adiabatic methanation reactor drum M1 and carry out first step methanation; The generation temperature is 400-650 ℃ first high-temperature gas 30; First high-temperature gas 30 reclaims reaction heat through the first heat recovery system WH1; The adjustment temperature exports the active starting temperature that the temperature that obtains the first methanation gas, 50, the first methanation gases 50 equals methanation catalyst; First part's fresh synthesis gas 40 that another road accounts for the 60-80V% of fresh synthesis gas volume mixes the back and gets into isothermal methanation reactor drum M2 and carry out second stage methanation with the first methanation gas 50; Generating temperature is 250-350 ℃ of second high-temperature gas 60; Second high-temperature gas 60 reclaims through second heat recovery system that to obtain temperature behind the reaction heat be 100-300 ℃ of product gas; Part product gas 70 is pressurized to fresh synthesis gas pressure as circulation gas through recycle compressor C1 or boosting jet pump E1; Circulation gets into the first adiabatic methanation reactor drum M1, and the product gas 80 of rest part is delivered to the 3rd heat recovery system WH3 in the methanation heat recovery steam-making device.The product gas 80 of part reclaims heat through the 3rd heat recovery system WH3; After the adjustment temperature, get into first gas-liquid separator 1 and carry out gas-liquid separation, gas separated 80a is through recycle compressor C2 compression; After the condensing surface CW heat exchange; Get into second gas-liquid separator 2 and carry out gas-liquid separation, the gas 80c after the separation is through after drying installation 3 dryings, again with sending into the SNG pipe network after the recycle compressor C3 compression.First gas-liquid separator 1 and second gas-liquid separator, 2 separation processes phlegma 80b, 80d send into phlegma treatment unit 200 after merging, through gas carry handle with thermal de-aeration after, as oiler feed.
In the fresh synthetic gas that comes out by the outlet of protection bed GB: H
2/ CO3.3～3.4V%, CO
21.5V%, CH
416.3V%, C2H4 (or C2H6 and C3H8) 0.2～0.6V%, N2/Ar0.2～0.6V%.Fresh synthesis gas through the outlet of overprotection bed GB is come out is the throughput ratio between adjustable first part fresh synthesis gas 10 and the second section fresh synthesis gas 40 through first variable valve 4 and second variable valve 5 that links.Circulation gas 70 can be regulated tolerance through recycle compressor C1 or boosting jet pump E1, and the tolerance that makes circulation gas 70 is 1.0 with the tolerance ratio of the product gas 80 that gets into methanation heat recovery steam-making device.The thermal insulation warming of controlling the first adiabatic methanation reactor drum M1 in the methanation device through the allocation proportion and the circulation gas flow of fresh synthesis gas is lower than the catalyzer maximum permisible service temperature; For example below 650 ℃; And the hot(test)-spot temperature of isothermal methanation reactor drum is carried out through flow and the drum pressure that control gets into the fresh synthesis gas of isothermal methanation reactor drum; Wherein hot(test)-spot temperature is 550-700 ℃, and drum pressure is 4.0-9.0MPa.
The isothermal methanation reactor drum M2 cold side of present embodiment adopts the boiler BFW and the service pump pump circulation type of cooling to remove heat.It is that 4.8MPa, temperature are 263 ℃ middle pressure saturation steam that boiler BFW adopts 90 ℃ of preheating de-salted waters to produce pressure, the flow 302000kg/h of 90 ℃ of preheating de-salted waters, the output 378000kg/h of middle pressure saturation steam.
The first adiabatic methanation reactor drum M1 of present embodiment can feed 90 ℃ of preheating de-salted waters, and to produce pressure be that 4.8MPa, temperature are 450 ℃ middle pressure superheated vapour; The flow 340000kg/h of 90 ℃ of preheating de-salted waters, the output 307000kg/h of middle pressure superheated vapour.
In the fresh synthesis gas that this embodiment adopts: H
2/ CO 3.3～3.4V%, CO
21.5V%, CH
416.3V%, C2H4 (or C2H6 and C3H8) 0.2～0.6V%, N2/Ar0.2～0.6V%.CH among the synthetic natural gas SNG that obtains
4Volume content is greater than 95% (or greater than 97.0%), H
2Less than 3.0% (or less than 1.0%), CO
2Less than 1%, CO is almost 0.
The resistance drop of the whole methanation step before the recycle compressor C2 is less than 5bar.
Identical as a comparison other technologies of scale can only be pressed superheated vapour: 273000kg/h (4.8MPa, 450 ℃) in the by-product; Whole methanation workshop section resistance drop is greater than 9bar.
Therefore adopt the isothermal methanation device of producing synthetic natural gas of present embodiment can many by-products superheated vapour, in year 80 yuan/t of benefit (307-273) t/h X X 8000h/=2,176 ten thousand Renminbi/years, economic benefit be considerable.
Methanation workshop section resistance reduces reducing investment of methane gas compressor and power consumption favourable.Practice thrift 0.5 yuan/Kwh of power consumption year benefit 1400Kwh X X 8000h/=5,600,000 Renminbi/years, economic benefit is considerable.
Embodiment 2
Present embodiment is identical with embodiment 1 basically, and difference is also to comprise a methanation refining plant, and this methanation refining plant is arranged between methanation device 100 and the methanation heat recovery steam-making device.Specifically be to set up one second adiabatic methanation reactor drum M3; The product gas 80 of rest part is delivered to the second adiabatic methanation reactor drum M3 earlier and is made with extra care; Product gas after refining is sent into the 3rd heat recovery system WH3 and is reclaimed heat, and the temperature of product gas is reduced.
Claims (15)
1. produce the isothermal methanation process of synthetic natural gas; Comprise methanation step, methanation heat recovery steam-making step and phlegma treatment step; Synthetic gas after the purification gets into the methanation step and carries out methanation, it is characterized in that said methanation step adopts the above methanation of secondary at least; Wherein first step methanation adopts the adiabatic methanation reactor drum to carry out methanation, and the subsequent stages methanation adopts the isothermal methanation reactor drum to carry out methanation;
Said methanation step is the secondary methanation;
Said secondary methanation concrete steps are: the synthetic gas after the purification is through overprotection bed GB; The total sulfur content that smart desulfurization to methanation catalyst can allow also is preheating to synthetic gas active starting temperature 200-300 ℃ of methanation catalyst; Obtain fresh synthetic gas and get into the methanation step, the pressure of fresh synthetic gas is 2.5-6.0MPa; The fresh synthetic gas that gets into the methanation step is divided into two-way; One the tunnel account for the 20-40V% of fresh synthetic gas volume the fresh synthetic gas of first part mix the back with circulation gas and get into the first adiabatic methanation reactor drum and carry out first step methanation to generate temperature be 400-650 ℃ first high-temperature gas; First high-temperature gas passes, first heat recovery system reclaims reaction heat and obtains the first methanation gas, and the temperature of the first methanation gas equals the active starting temperature of methanation catalyst; The fresh synthetic gas of second section that another road accounts for the 60-80V% of fresh synthetic gas volume mixes the back and gets into the isothermal methanation reactor drum and carry out second stage methanation to generate temperature be 250-350 ℃ of second high-temperature gas with the first methanation gas; Obtaining temperature behind second high-temperature gas passes, second heat recovery system recovery reaction heat is 100～300 ℃ of product gas; A product gas part is delivered to the first adiabatic methanation reactor drum as circulation gas through being pressurized to fresh synthetic gas pressure, and rest part is delivered to methanation heat recovery steam-making step;
In the said fresh synthetic gas: H
2/ CO 3.3～3.4V%, CO
21.5V%, CH
416.3V%, C
2H
40.2～0.6V% or C
2H6 and C
3H
80.2～0.6V%, N
2/ Ar 0.2～0.6V%.
2. the isothermal methanation process of producing synthetic natural gas as claimed in claim 1 is characterized in that, protection bed GB is normal temperature protection bed or high temperature protection bed.
3. the isothermal methanation process of producing synthetic natural gas as claimed in claim 1; It is characterized in that; Control the temperature out of adiabatic methanation reactor drum through the tolerance of Control Circulation gas; Make 650-700 ℃ of the permission service temperature that it is lower than methanation catalyst, wherein the tolerance of circulation gas is 0.5-1.5 with the tolerance ratio of the product gas that gets into methanation heat recovery steam-making step.
4. the isothermal methanation process of producing synthetic natural gas as claimed in claim 1; It is characterized in that; The hot(test)-spot temperature of said isothermal methanation reactor drum is carried out through flow and the drum pressure that control gets into the fresh synthetic gas of isothermal methanation reactor drum; Wherein hot(test)-spot temperature is 550-700 ℃, and drum pressure is 4.0-9.0MPa.
5. the isothermal methanation process of producing synthetic natural gas as claimed in claim 1; It is characterized in that; Said isothermal methanation reactor drum cold side adopts the boiler and the service pump pump circulation type of cooling to remove heat, and the middle pressure saturation steam of while by-product 4.0-9.0MPa.
6. the isothermal methanation process of producing synthetic natural gas as claimed in claim 1 is characterized in that, the said first adiabatic methanation reactor drum can be pressed superheated vapour among the by-product 4.0-9.0MPa.
7. the isothermal methanation process of producing synthetic natural gas as claimed in claim 1 is characterized in that, said circulation gas adopts recycle compressor or boosting jet pump to carry out supercharging.
8. the isothermal methanation process of producing synthetic natural gas as claimed in claim 1 is characterized in that the resistance drop of said whole methanation step is less than 5bar.
9. the isothermal methanation process of producing synthetic natural gas as claimed in claim 1; It is characterized in that; Comprise that also one is arranged on the methanation purification step between methanation step and the methanation heat recovery steam-making step; The product gas of being come by the methanation step at first gets into the second adiabatic methanation reactor drum, and to carry out methanation refining, and the product gas after refining is sent into methanation heat recovery steam-making step.
10. realize the described isothermal methanation device of producing the isothermal methanation process of synthetic natural gas of claim 1 for one kind; Comprise protection bed GB, methanation device, methanation heat recovery steam-making device and phlegma treatment unit; It is characterized in that said methanation device comprises one first adiabatic methanation reactor drum, isothermal methanation reactor drum, first HRU, second HRU, supercharging circulation device; The outlet of said protection bed is divided into the two-way pipeline; Wherein first via pipeline connects the inlet of the first adiabatic methanation reactor drum; The outlet of second pipeline and first HRU and connect after connect the inlet of isothermal methanation reactor drum; The outlet of adiabatic methanation reactor drum connects the inlet of first HRU, and the outlet of isothermal methanation reactor drum connects the inlet of second HRU, and the outlet of second HRU is divided into two-way; One the tunnel connects methanation heat recovery steam-making device, and another road connects the inlet of the first adiabatic methanation reactor drum through the supercharging circulation device;
Said isothermal methanation process comprises methanation step, methanation heat recovery steam-making step and phlegma treatment step; Synthetic gas after the purification gets into the methanation step and carries out methanation; It is characterized in that; Said methanation step adopts the above methanation of secondary at least, and wherein first step methanation adopts the adiabatic methanation reactor drum to carry out methanation, and the subsequent stages methanation adopts the isothermal methanation reactor drum to carry out methanation;
Said methanation step is the secondary methanation;
Said secondary methanation concrete steps are: the synthetic gas after the purification is through overprotection bed GB; The total sulfur content that smart desulfurization to methanation catalyst can allow also is preheating to synthetic gas active starting temperature 200-300 ℃ of methanation catalyst; The synthetic gas that obtains desulfurization gets into the methanation step, and the pressure of the synthetic gas of desulfurization is 2.5-6.0MPa; The synthetic gas that gets into the desulfurization of methanation step is divided into two-way; One the tunnel account for the synthetic gas volume of desulfurization the synthetic gas of first part's desulfurization of 20-40V% mix the back with circulation gas and get into the first adiabatic methanation reactor drum and carry out first step methanation to generate temperature be 400-650 ℃ first high-temperature gas; First high-temperature gas passes, first heat recovery system reclaims reaction heat and obtains the first methanation gas, and the temperature of the first methanation gas equals the active starting temperature of methanation catalyst; The synthetic gas of second section desulfurization of 60-80V% that another road accounts for the synthetic gas volume of desulfurization mixes the back and gets into the isothermal methanation reactor drum and carry out second stage methanation to generate temperature be 250-350 ℃ of second high-temperature gas with the first methanation gas; Obtaining temperature behind second high-temperature gas passes, second heat recovery system recovery reaction heat is 100～300 ℃ of product gas; A product gas part is delivered to the first adiabatic methanation reactor drum as circulation gas through the synthetic gas pressure that is pressurized to desulfurization, and rest part is delivered to methanation heat recovery steam-making step;
In the said fresh synthetic gas: H
2/ CO 3.3～3.4V%, CO
21.5V%, CH
416.3V%, C
2H
40.2～0.6V% or C
2H6 and C
3H
80.2～0.6V%, N
2/ Ar 0.2～0.6V%.
11. isothermal methanation device as claimed in claim 10; It is characterized in that; The cold side of said isothermal methanation reactor drum connects a boiler, and said boiler is through pump circulation between service pump and the isothermal methanation reactor drum, the middle pressure saturation steam of by-product 4.0-9.0MPa simultaneously.
12. isothermal methanation device as claimed in claim 10; It is characterized in that; The first via pipeline of the outlet of protection bed is provided with first variable valve; The second road pipeline is provided with second variable valve, is the throughput ratio of fresh synthesis gas in the adjustable first via pipeline and the second road pipeline through first variable valve and the interlock of second variable valve.
13. isothermal methanation device as claimed in claim 10 is characterized in that, said supercharging circulation device is recycle compressor or boosting jet pump.
14. isothermal methanation device as claimed in claim 10 is characterized in that, also comprises a methanation refining plant, this methanation refining plant is arranged between said methanation device and the methanation heat recovery steam-making device.
15. isothermal methanation device as claimed in claim 14; It is characterized in that; Said methanation refining plant comprises the second adiabatic methanation reactor drum, and the inlet of the second adiabatic methanation reactor drum connects a way outlet of second HRU, and outlet connects methanation heat recovery steam-making device.
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| US10233078B2 (en) | 2012-12-18 | 2019-03-19 | Basf Se | Process for utilizing blast furnace gases, associated gases and/or biogases |
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| CN101880559B (en) * | 2010-06-18 | 2013-01-23 | 大唐国际化工技术研究院有限公司 | Method and device for producing synthetic natural gas |
| CN102311096B (en) * | 2010-06-29 | 2013-08-14 | 中国石油化工股份有限公司 | Method for deeply removing CO and CO2 in ethylene and synthesis ammonia process |
| CN102041120B (en) * | 2010-12-15 | 2013-06-12 | 新奥科技发展有限公司 | Method for generating synthetic natural gas |
| CN103242921B (en) * | 2012-02-09 | 2014-12-10 | 中国科学院大连化学物理研究所 | Technology for preparing natural gas from synthetic gas |
| CN102757016B (en) * | 2012-07-20 | 2015-04-22 | 上海国际化建工程咨询公司 | Method and device for cogeneration of synthesis ammonia gas and liquefied natural gas prepared through pressure gasification of crushed coal in fixed bed |
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| CN103695058B (en) * | 2013-12-19 | 2015-05-20 | 中国海洋石油总公司 | Novel methanation reaction process for preparing synthetic natural gas |
| CN103820183B (en) * | 2014-02-26 | 2016-08-31 | 山西华兆煤化工有限责任公司 | A kind of oven gas directly mends the method for carbon dioxide synthetic natural gas |
| CN105087091B (en) * | 2014-05-08 | 2017-09-05 | 中国石油化工股份有限公司 | A kind of technique for preparing synthetic natural gas |
| CN107227184B (en) * | 2016-03-23 | 2019-10-08 | 中国石化工程建设有限公司 | A kind of system and technique producing substitution natural gas |
| CN109593581A (en) * | 2018-12-21 | 2019-04-09 | 惠生工程（中国）有限公司 | It is a kind of once to pass through methanation process |
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