CN101705128A - Adiabatic methanation process and device for preparing synthetic natural gas - Google Patents
Adiabatic methanation process and device for preparing synthetic natural gas Download PDFInfo
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- CN101705128A CN101705128A CN 200910054770 CN200910054770A CN101705128A CN 101705128 A CN101705128 A CN 101705128A CN 200910054770 CN200910054770 CN 200910054770 CN 200910054770 A CN200910054770 A CN 200910054770A CN 101705128 A CN101705128 A CN 101705128A
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Abstract
The invention discloses an adiabatic methanation process for preparing synthetic natural gas, which comprises the following steps of: carrying out methanation; carrying out methanation heat recovery to prepare steam; and processing a condensate, wherein purified synthesis gas enters the methanation step to carry out methanation. The process is characterized in that: the methanation step adopts at least one adiabatic methanation reactor to carry out methanation and also comprises a methanation refining step; and the methanation refining step is arranged between the methanation step and the step of methanation heat recovery to prepare the steam or arranged in the step of the methanation heat recovery to prepare the steam. The invention also discloses an adiabatic methanation device used for an isothermal methanation process for preparing the synthetic natural gas. The process and the device have the advantages of energy saving, environmental protection and less 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, adiabatic 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 directly to do fuel at present, and utilising efficiency is low; And coal is in combustion processes, discharge a large amount of waste gas, objectionable impuritiess such as waste residue, polluted air, waters and soil, carbon---the coal that chemical industry is used all is by railway and ship transportation in addition, carriage load is heavy, 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 is through modified (adjustment gaseous constituent), purify (removing the poisonous impurity of methanation catalyst), 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.
To help 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 shortcoming such as the methane gas that adopts external existing industrialized unit to make exists that carbon content height, hydrogen richness height, calorific value are low, of poor quality, heat recovery efficiency difference and flow process complexity, 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 as follows:
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.By above-mentioned reaction formula as can be seen, methanation reaction is a strong exothermal reaction, and 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, discharge a large amount of heats, one-pass thermal insulation warming can reach 400～600 ℃, is very easy to cause the inactivation of catalyzer and reactor 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 are the following problems in the methanation process at present:
1. existing methanation process complexity, methanator quantity is many, and heat-exchange equipment is many;
2. internal circulating load is big, the circulating consumption height, and single cover maximizes difficult;
3. adopt high-temperature gas round-robin methanation process at present, recycle compressor manufactures and designs difficult, the operational conditions harshness, 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 adiabatic methanation process of producing synthetic natural gas, its by to the methanator texture improvement, move hot mode improvement, shunting, cold shock and other means gas-circulating system improved, adopt isothermal methanation reactor bound gas circulation technology, by 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 adiabatic methanation device of producing synthetic natural gas of above-mentioned technology.
The adiabatic 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 enters the methanation step and carries out methanation, it is characterized in that described methanation step adopts above at least adiabatic methanation reactor to carry out methanation; Also comprise the methanation purification step, this methanation purification step is arranged between described methanation step and the methanation heat recovery steam-making step or is arranged in the methanation heat recovery steam-making step.
Methanation step of the present invention is specifically: 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 200～300 ℃ of the active starting temperatures of methanation catalyst, fresh synthetic gas enters the methanation step, the fresh synthesis gas that enters the methanation step is divided into two-way, one the tunnel account for the fresh synthesis gas volume 40-70V% first part's fresh synthesis gas with enter the first adiabatic methanation reactor after circulation gas mixes 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 active starting temperature 200-300 ℃ of methanation catalyst; Another road account for the fresh synthesis gas volume 30-60V% the second section fresh synthesis gas with enter the second adiabatic methanation reactor after the first methanation gas mixes and carry out second stage methanation to generate temperature be 400-650 ℃ of second high-temperature 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 as circulation gas through being pressurized to the fresh synthesis gas atmospheric 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 the first adiabatic methanation reactor by 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 2.0-5.0 with the tolerance ratio that enters the product gas of methanation heat recovery steam-making step.
In aforesaid method, the hot(test)-spot temperature of the second adiabatic methanation reactor enters the fresh synthesis gas of the second adiabatic methanation reactor by control flow carries out.
In aforesaid method, the first adiabatic methanation reactor and the second adiabatic methanation reactor can be pressed superheated vapour among the by-product 4.0-9.0MPa.
In aforesaid method, in the described 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, the methanation purification step that is arranged between described methanation step and the methanation heat recovery steam-making step adopts an isothermal methanation reactor and one the 3rd heat recovery system to realize, the product gas of rest part is introduced into the isothermal methanation reactor and makes with extra care, product gas after refining reclaims heat by the 3rd heat recovery system again, sends into methanation heat recovery steam-making step behind the attemperation.
In aforesaid method, the methanation purification step that is arranged between described methanation step and the methanation heat recovery steam-making step adopts the 3rd adiabatic methanation reactor, the 4th adiabatic methanation reactor and the 3rd heat recovery system, the 4th heat recovery system realizes, the product gas of rest part is introduced into the 3rd adiabatic methanation reactor and makes with extra care, product gas after refining reclaims heat by the 3rd heat recovery system again, sending into the 4th adiabatic methanation reactor behind the attemperation again carries out further refining, product gas after further refining reclaims heat by the 4th heat recovery system again, sends into methanation heat recovery steam-making step behind the attemperation.
In aforesaid method, be arranged on the 3rd adiabatic methanation reactor after methanation purification step in the methanation heat recovery steam-making step adopts the first step loop compression be arranged in the methanation heat recovery steam-making step, the 3rd heat recovery system realizes, through the first step gas-liquid separation, product gas after the first step loop compression enters the 3rd adiabatic methanation reactor after by the product gas heat exchange of coming out with the 3rd adiabatic methanation reactor and carries out further refining, product gas after further refining by with through the first step gas-liquid separation, enter the 3rd heat recovery system after the product gas heat exchange after the first step loop compression and reclaim heat, enter the second step gas-liquid separation behind the attemperation and carry out gas-liquid separation, send into moisture eliminator through the gas after the second step gas-liquid separation and carry out drying.
The adiabatic 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; also comprise a methanation refining plant, described methanation refining plant is arranged between methanation device and the methanation heat recovery steam-making device or is arranged in the methanation heat recovery steam-making device.
Methanation device of the present invention comprises the first adiabatic methanation reactor, the second adiabatic methanation reactor, first heat reclamation device, second heat reclamation device, supercharging circulation device; The outlet of described protection bed is divided into the two-way pipeline; wherein first via pipeline connects the inlet of the first adiabatic methanation reactor; the outlet of second pipeline and first heat reclamation device and connect after connect the inlet of the second adiabatic methanation reactor; the outlet of the first adiabatic methanation reactor connects the inlet of first heat reclamation device; the outlet of the second adiabatic methanation reactor connects the inlet of second heat reclamation device; the outlet of second heat reclamation device is divided into two-way; one the tunnel connects methanation heat recovery steam-making device or methanation refining plant, and another road connects the inlet of the first adiabatic methanation reactor by the supercharging circulation device.
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, the throughput ratio that can regulate fresh synthesis gas in the first via pipeline and the second road pipeline by first variable valve and second variable valve.
Described supercharging circulation device is recycle compressor or boosting jet pump.
The described methanation refining plant that is arranged between methanation device and the methanation heat recovery steam-making device comprises an isothermal methanation reactor and the 3rd heat reclamation device, one way outlet of second heat reclamation device connects the inlet of isothermal methanation reactor, the outlet of isothermal methanation reactor connects the inlet of the 3rd heat reclamation device, and the outlet of the 3rd heat reclamation device connects methanation heat recovery steam-making device.
The described methanation refining plant that is arranged between methanation device and the methanation heat recovery steam-making device comprises the 3rd adiabatic methanation reactor, the 4th adiabatic methanation reactor, the 3rd heat reclamation device, the 4th heat reclamation device, one way outlet of second heat reclamation device connects the inlet of the 3rd adiabatic methanation reactor, the outlet of the 3rd adiabatic methanation reactor connects the inlet of the 3rd heat reclamation device, the outlet of the 3rd heat reclamation device connects the inlet of the 4th adiabatic methanation reactor, the outlet of the 4th adiabatic methanation reactor connects the inlet of the 4th heat reclamation device, and the outlet of the 4th heat reclamation device connects methanation heat recovery steam-making device.
The described methanation refining plant that is arranged in the methanation heat recovery steam-making device comprises the 3rd adiabatic methanation reactor and the 3rd heat reclamation device, and this methanation heat recovery steam-making device comprises the 4th heat reclamation device, first gas-liquid separator, second recycle compressor, heat exchanger, second gas-liquid separator, moisture eliminator, the 3rd recycle compressor, one way outlet of second heat reclamation device connects the inlet of the 4th heat reclamation device, the outlet of the 4th heat reclamation device connects the inlet of first gas-liquid separator, the pneumatic outlet of first gas-liquid separator connects the inlet of second recycle compressor, the outlet of second recycle compressor connects the inlet of the 3rd adiabatic methanation reactor by heat exchanger, the outlet of the 3rd adiabatic methanation reactor is by connecing the inlet of the 3rd heat reclamation device by heat exchanger, the outlet of the 3rd heat reclamation device connects the inlet of second gas-liquid separator, the pneumatic outlet of second gas-liquid separator connects the inlet of moisture eliminator, the outlet of moisture eliminator connects the SNG pipe network, the liquid exit of the liquid exit of first gas-liquid separator and second gas-liquid separator connects the inlet of phlegma treatment unit simultaneously, and the outlet of phlegma treatment unit connects boiler.
The present invention is by discovering: temperature of reaction has the greatest impact to methanation reaction, though the temperature of reaction height, byproduct steam pressure rating height, Btu utilization efficient height.If but circulation gas temperature height, harsh to the operational conditions requirement of recycle compressor, power consumption is big; And the temperature of reaction height, whole methanation device needs particular design, to catalyst tolerates heat request height, steam content is also had requirement.And in research process, find, suitably reduce circulating flow rate and improve entering 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 responsive more to poisonous substance, so the methanation reaction temperature also should not be low excessively.The present invention is by discovering the high nickel content methanation catalyst when temperature is too low, carbonylation and low-temperature inactive easily, and when temperature is too high, sintering inactivation and analyse the carbon reaction easily.
In addition, the present invention is by discovering, pressure also is an important index to methanation reaction, 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.Find in research process: 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 the high more easy more generation metal dusting corrosion of CO content, 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.
The present invention by discovering methane in the fresh synthesis gas content and the water yield of generation certain relation is arranged, methane content is low in the synthetic gas, 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 the methane content height, help reducing response intensity, prolong the work-ing life of catalyzer.
Based on above research, the present invention is under the prerequisite that the loop compression equipment design is made and operation allows, improving the temperature of circulation gas as far as possible,, reduce the long-time running expense to improve heat recovery efficiency. the present invention adopts isothermal methanation, avoided causing investment of methane gas (SNG) compressor and power consumption significantly to increase, simultaneously can the by-product saturation steam, as the power steam use, can effectively reduce internal circulating load through overheated back, simplify flow process, improve 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 GB17820-1999 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, investment and the loss of avoiding long distance to carry.
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 carbonaceous materials such as coal or biomass, be applicable to powdered coal pressuring gasified (as SHELL gasification, GSP gasification, E-GAS gasification etc.), water coal slurry pressure gasification (as GE gasification, polynary slurry gasification, the gasification of opposed type burner etc.) or fixed bed pressured gasification (as the gasification of LURGI dry bottom bed 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 the drawings and specific embodiments.
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.
Fig. 3 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 readily clear of 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 adiabatic methanation device of synthetic natural gas, comprise protection bed GB, methanation device 100, methanation refining plant 200, methanation heat recovery steam-making device and phlegma treatment unit 300.Methanation device comprises the first adiabatic methanation reactor M1, the first adiabatic methanation reactor M2, the first heat recovery system WH1, the second heat recovery system WH2, the first recycle compressor C1; Methanation heat recovery steam-making device comprises the 4th heat recovery system WH4, first knockout drum 1, the second recycle compressor C2, condenser CW, second knockout drum 2, moisture eliminator 3, the 3rd recycle compressor C3.Methanation refining plant 200 comprises the 3rd adiabatic methanation reactor M3 and the 3rd heat recovery system WH3.
Raw gas is regulated (H through conversion
2-CO
2)/(CO+CO
2) be slightly larger than 3, enter 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 can allow to methanation catalyst 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 poisonous substance of the methanation catalyst that workshop section brings into before overprotection bed GB removes is as 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 fresh synthesis gas volume 40-70V% first part's fresh synthesis gas 10 with enter the first adiabatic methanation reactor M1 after circulation gas 20 mixes 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, adjust temperature, the temperature that outlet obtains the first methanation gas, 50, the first methanation gases 50 equals active starting temperature 200-300 ℃ of methanation catalyst; Another road account for the fresh synthesis gas volume 30-60V% second section fresh synthesis gas 40 with enter the second adiabatic methanation reactor M2 after the first methanation gas 50 mixes and carry out second stage methanation, generating temperature is 400-650 ℃ 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 the fresh synthesis gas pressure cycling as circulation gas through recycle compressor C1 or boosting jet pump E1 and enters the first adiabatic methanation reactor M1, and the product gas 80 of rest part is delivered to the 4th heat recovery system WH4.The product gas 80 of part reclaims heat through the 4th heat recovery system WH4, after adjusting temperature, enter first gas-liquid separator 1 and carry out gas-liquid separation, gas separated 80a is through recycle compressor C2 compression, after the purified product gas heat exchange of coming out by the 3rd adiabatic methanation reactor in heat exchanger CW and the methanation refining plant, enter in the 3rd adiabatic methanation reactor and make with extra care, product gas after refining is by after the heat exchanger CW heat exchange, enter the 3rd heat recovery system WH3 and reclaim heat, enter second gas-liquid separator 2 behind the attemperation and carry out gas-liquid separation, gas 80c after the separation is by 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 300 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%.
Can regulate throughput ratio between first part's fresh synthesis gas 10 and the second section fresh synthesis gas 40 through fresh synthesis gas that the outlet of overprotection bed GB is come out first variable valve 4 and second variable valve 5 by interlock.Circulation gas 70 can be regulated tolerance by recycle compressor C1 or boosting jet pump E1, and making the tolerance of circulation gas 70 and the tolerance ratio that enters the product gas 80 of methanation heat recovery steam-making device is 3.0.The thermal insulation warming of controlling the first adiabatic methanation reactor M1 in the methanation device by 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 the second adiabatic methanation reactor M2 is undertaken by the flow that control enters the fresh synthesis gas of the second adiabatic methanation reactor, and wherein hot(test)-spot temperature is 550-700 ℃.
The first adiabatic methanation reactor M1 of present embodiment, the second adiabatic methanation reactor M2, the 3rd adiabatic methanation reactor M3 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 540000kg/h of 90 ℃ of preheating de-salted waters, the output 306000kg/h of middle pressure superheated vapour.Perhaps feeding 90 ℃ of preheating de-salted waters, to produce pressure be that 4.8MPa, temperature are 263 ℃ middle pressure saturation steam, the flow 490000kg/h of 90 ℃ of preheating de-salted waters, the output 380000kg/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 (306-273) t/h X X 8000h/=2,112 ten thousand Renminbi/years, economic benefit be considerable.
Methanation workshop section resistance reduces reducing investment of methane gas compressor and power consumption favourable.Save 0.5 yuan/Kwh of power consumption year benefit 1400Kwh X X 8000h/=5,600,000 Renminbi/years, economic benefit is considerable.
Embodiment 2
Referring to Fig. 2, produce the adiabatic methanation device of synthetic natural gas, comprise protection bed GB, methanation device 100, methanation refining plant 200, methanation heat recovery steam-making device and phlegma treatment unit 300.Methanation device comprises the first adiabatic methanation reactor M1, the first adiabatic methanation reactor M2, the first heat recovery system WH1, the second heat recovery system WH2, the first recycle compressor C1; Methanation heat recovery steam-making device comprises first knockout drum 1, the second recycle compressor C2, condenser CW, second knockout drum 2, moisture eliminator 3, the 3rd recycle compressor C3.Methanation refining plant 200 comprises isothermal methanation reactor M5 and the 3rd heat recovery system WH3.
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 fresh synthesis gas volume 40-70V% first part's fresh synthesis gas 10 with enter the first adiabatic methanation reactor M1 after circulation gas 20 mixes 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, adjust temperature, outlet obtains the first methanation gas 50, the temperature of the first methanation gas 50 equals the active starting temperature of methanation catalyst, and pressure is 200-300 ℃; Another road account for the fresh synthesis gas volume 30-60V% second section fresh synthesis gas 40 with enter the second adiabatic methanation reactor M2 after the first methanation gas 50 mixes and carry out second stage methanation, generating temperature is 400-650 ℃ 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 the fresh synthesis gas pressure cycling as circulation gas through recycle compressor C1 or boosting jet pump E1 and enters the first adiabatic methanation reactor M1, the isothermal methanation reactor M5 that the product gas 80 of rest part is delivered to the methanation refining plant makes with extra care, be admitted to the 3rd heat reclamation device WH3 through the purified product gas and reclaim heat, enter first gas-liquid separator 1 behind the attemperation and carry out gas-liquid separation, gas separated 80a is through recycle compressor C2 compression, carry out heat exchange by heat exchanger, product gas after the heat exchange is admitted to second gas-liquid separator and carries out gas-liquid separation once more, gas 80c after the separation is by 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 sends into phlegma treatment unit 300 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%.
Can regulate throughput ratio between first part's fresh synthesis gas 10 and the second section fresh synthesis gas 40 through fresh synthesis gas that the outlet of overprotection bed GB is come out first variable valve 4 and second variable valve 5 by interlock.Circulation gas 70 can be regulated tolerance by recycle compressor C1 or boosting jet pump E1, and making the tolerance of circulation gas 70 and the tolerance ratio that enters the product gas 80 of methanation heat recovery steam-making device is 3.0.The thermal insulation warming of controlling the first adiabatic methanation reactor M1 in the methanation device by 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 the second adiabatic methanation reactor M2 is undertaken by the flow that control enters the fresh synthesis gas of the second adiabatic methanation reactor, and wherein hot(test)-spot temperature is 550-700 ℃.
The first adiabatic methanation reactor M1 of present embodiment, the second adiabatic methanation reactor M2 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 540000kg/h of 90 ℃ of preheating de-salted waters, the output 306000kg/h of middle pressure superheated vapour.Isothermal methanation reactor M5 can feed 90 ℃ of preheating de-salted waters, and to produce pressure be that 4.8MPa, temperature are 263 ℃ middle pressure saturation steam, the flow 490000kg/h of 90 ℃ of preheating de-salted waters, the output 380000kg/h of middle pressure superheated vapour.Isothermal methanation reactor M5 page or leaf can adopt air cooling isothermal pattern.
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 (306-273) t/h X X 8000h/=2,112 ten thousand Renminbi/years, economic benefit be considerable.
Methanation workshop section resistance reduces reducing investment of methane gas compressor and power consumption favourable.Save 0.5 yuan/Kwh of power consumption year benefit 1400Kwh X X 8000h/=5,600,000 Renminbi/years, economic benefit is considerable.
Referring to Fig. 3, produce the adiabatic methanation device of synthetic natural gas, comprise that protection bed GB, methanation device 100, methanation refining plant 200, methanation heat recovery steam-making device and phlegma treatment unit 300. methanation devices comprise the first adiabatic methanation reactor M1, the first adiabatic methanation reactor M2, the first heat recovery system WH1, the second heat recovery system WH2, the first recycle compressor C1; Methanation heat recovery steam-making device comprises that first knockout drum 1, the second recycle compressor C2, condenser CW, second knockout drum 2, moisture eliminator 3, the 3rd recycle compressor C3. methanation refining plant 200 comprise the 3rd adiabatic methanation reactor M3, the 4th adiabatic methanation reactor M4, the 3rd heat reclamation device WH3, the 4th heat reclamation device WH4.
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 fresh synthesis gas volume 40-70V% first part's fresh synthesis gas 10 with enter the first adiabatic methanation reactor M1 after circulation gas 20 mixes 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, adjust temperature, the temperature that outlet obtains the first methanation gas, 50, the first methanation gases 50 equals active starting temperature 200-300 ℃ of methanation catalyst; Another road account for the fresh synthesis gas volume 30-60V% second section fresh synthesis gas 40 with enter the second adiabatic methanation reactor M2 after the first methanation gas 50 mixes and carry out second stage methanation, generating temperature is 400-650 ℃ 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 the fresh synthesis gas pressure cycling as circulation gas through recycle compressor C1 or boosting jet pump E1 and enters the first adiabatic methanation reactor M1, it is refining that the 3rd adiabatic methanation reactor M3 that the product gas 80 of rest part is delivered to the methanation refining plant carries out the first step, be admitted to the 3rd heat reclamation device WH3 through the first step purified product gas and reclaim heat, be admitted to the 4th adiabatic methanation reactor M4 behind the attemperation again and carry out second one-step refining, send into the 4th heat reclamation device WH4 through the product gas behind second one-step refining and reclaim heat, enter first gas-liquid separator 1 behind the attemperation and carry out gas-liquid separation, gas separated 80a is through recycle compressor C2 compression, carry out heat exchange by heat exchanger, product gas after the heat exchange is admitted to second gas-liquid separator and carries out gas-liquid separation once more, gas 80c after the separation is by 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 300 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%.
Can regulate throughput ratio between first part's fresh synthesis gas 10 and the second section fresh synthesis gas 40 through fresh synthesis gas that the outlet of overprotection bed GB is come out first variable valve 4 and second variable valve 5 by interlock.Circulation gas 70 can be regulated tolerance by recycle compressor C1 or boosting jet pump E1, and making the tolerance of circulation gas 70 and the tolerance ratio that enters the product gas 80 of methanation heat recovery steam-making device is 3.0.The thermal insulation warming of controlling the first adiabatic methanation reactor M1 in the methanation device by 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 the second adiabatic methanation reactor M2 is undertaken by the flow that control enters the fresh synthesis gas of the second adiabatic methanation reactor, and wherein hot(test)-spot temperature is 550-700 ℃.
The first adiabatic methanation reactor M1 of present embodiment, the second adiabatic methanation reactor M2, the 3rd adiabatic methanation reactor M3, the 4th adiabatic methanation reactor M4 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 540000kg/h of 90 ℃ of preheating de-salted waters, the output 306000kg/h of middle pressure superheated vapour.Perhaps feeding 90 ℃ of preheating de-salted waters, to produce pressure be that 4.8MPa, temperature are 263 ℃ middle pressure saturation steam, the flow 490000kg/h of 90 ℃ of preheating de-salted waters, the output 380000kg/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 (306-273) t/h X X 8000h/=2,112 ten thousand Renminbi/years, economic benefit be considerable.
Methanation workshop section resistance reduces reducing investment of methane gas compressor and power consumption favourable.Save power consumption year benefit.
Claims (19)
1. produce the adiabatic methanation process of synthetic natural gas, comprise methanation step, methanation heat recovery steam-making step and phlegma treatment step, synthetic gas after the purification enters the methanation step and carries out methanation, it is characterized in that described methanation step adopts above at least adiabatic methanation reactor to carry out methanation; Also comprise the methanation purification step, this methanation purification step is arranged between described methanation step and the methanation heat recovery steam-making step or is arranged in the methanation heat recovery steam-making step.
2. the adiabatic methanation process of producing synthetic natural gas as claimed in claim 1, it is characterized in that, described methanation step is specifically: 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 active starting temperature 200-300 ℃ of methanation catalyst with synthetic gas and obtains fresh synthetic gas and enter the methanation step, and the pressure of fresh synthetic gas is 2.5-6.0MPa; The fresh synthesis gas that enters the methanation step is divided into two-way, one the tunnel account for the fresh synthesis gas volume 40-70V% first part's fresh synthesis gas with enter the first adiabatic methanation reactor after circulation gas mixes 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 active starting temperature 200-300 ℃ of methanation catalyst; Another road account for the fresh synthesis gas volume 30-60V% the second section fresh synthesis gas with enter the second adiabatic methanation reactor after the first methanation gas mixes and carry out second stage methanation to generate temperature be 400-650 ℃ of second high-temperature gas, second high-temperature gas passes, second heat recovery system reclaims and to obtain temperature behind the reaction heat is 100-300 ℃ product gas, a product gas part is delivered to the first adiabatic methanation reactor as circulation gas through being pressurized to fresh synthesis gas pressure, and rest part is delivered to methanation heat recovery steam-making step.
3. the adiabatic methanation process of producing synthetic natural gas as claimed in claim 2 is characterized in that, protection bed GB is normal temperature protection bed or high temperature protection bed.
4. the adiabatic methanation process of producing synthetic natural gas as claimed in claim 2, it is characterized in that, control the temperature out of the first adiabatic methanation reactor by 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 2.0-5.0 with the tolerance ratio that enters the product gas of methanation heat recovery steam-making step.
5. the adiabatic methanation process of producing synthetic natural gas as claimed in claim 2 is characterized in that the hot(test)-spot temperature of the second adiabatic methanation reactor is undertaken by the flow that control enters the fresh synthesis gas of the second adiabatic methanation reactor.
6. the adiabatic methanation process of producing synthetic natural gas as claimed in claim 2 is characterized in that, the first adiabatic methanation reactor and the second adiabatic methanation reactor can be pressed superheated vapour among the by-product 4.0-9.0MPa.
7. the adiabatic methanation process of producing synthetic natural gas as claimed in claim 2 is characterized in that, in the described 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%.
8. the adiabatic methanation process of producing synthetic natural gas as claimed in claim 2 is characterized in that, circulation gas adopts recycle compressor or boosting jet pump to carry out supercharging.
9. the adiabatic methanation process of producing synthetic natural gas as claimed in claim 2 is characterized in that the resistance drop of whole methanation step is less than 5bar.
10. the adiabatic methanation process of producing synthetic natural gas as claimed in claim 2, it is characterized in that, the methanation purification step that is arranged between described methanation step and the methanation heat recovery steam-making step adopts an isothermal methanation reactor and one the 3rd heat recovery system to realize, the product gas of rest part is introduced into the isothermal methanation reactor and makes with extra care, product gas after refining reclaims heat by the 3rd heat recovery system again, sends into methanation heat recovery steam-making step behind the attemperation.
11. the adiabatic methanation process of producing synthetic natural gas as claimed in claim 2, it is characterized in that, the methanation purification step that is arranged between described methanation step and the methanation heat recovery steam-making step adopts the 3rd adiabatic methanation reactor, the 4th adiabatic methanation reactor and the 3rd heat recovery system, the 4th heat recovery system realizes, the product gas of rest part is introduced into the 3rd adiabatic methanation reactor and makes with extra care, product gas after refining reclaims heat by the 3rd heat recovery system again, sending into the 4th adiabatic methanation reactor behind the attemperation again carries out further refining, product gas after further refining reclaims heat by the 4th heat recovery system again, sends into methanation heat recovery steam-making step behind the attemperation.
12. the adiabatic methanation process of producing synthetic natural gas as claimed in claim 2, it is characterized in that, be arranged on the 3rd adiabatic methanation reactor after methanation purification step in the methanation heat recovery steam-making step adopts the first step loop compression be arranged in the methanation heat recovery steam-making step, the 3rd heat recovery system realizes, through the first step gas-liquid separation, product gas after the first step loop compression enters the 3rd adiabatic methanation reactor after by the product gas heat exchange of coming out with the 3rd adiabatic methanation reactor and carries out further refining, product gas after further refining by with through the first step gas-liquid separation, enter the 3rd heat recovery system after the product gas heat exchange after the first step loop compression and reclaim heat, enter the second step gas-liquid separation behind the attemperation and carry out gas-liquid separation, send into moisture eliminator through the gas after the second step gas-liquid separation and carry out drying.
13. adiabatic methanation device of producing synthetic natural gas; comprise protection bed GB, methanation device, methanation heat recovery steam-making device and phlegma treatment unit; it is characterized in that; also comprise a methanation refining plant, described methanation refining plant is arranged between methanation device and the methanation heat recovery steam-making device or is arranged in the methanation heat recovery steam-making device.
14. the adiabatic methanation device of producing synthetic natural gas as claimed in claim 13, it is characterized in that described methanation device comprises the first adiabatic methanation reactor, the second adiabatic methanation reactor, first heat reclamation device, second heat reclamation device, supercharging circulation device; The outlet of described protection bed is divided into the two-way pipeline; wherein first via pipeline connects the inlet of the first adiabatic methanation reactor; the outlet of second pipeline and first heat reclamation device and connect after connect the inlet of the second adiabatic methanation reactor; the outlet of the first adiabatic methanation reactor connects the inlet of first heat reclamation device; the outlet of the second adiabatic methanation reactor connects the inlet of second heat reclamation device; the outlet of second heat reclamation device is divided into two-way; one the tunnel connects methanation heat recovery steam-making device or methanation refining plant, and another road connects the inlet of the first adiabatic methanation reactor by the supercharging circulation device.
15. the adiabatic methanation device of producing synthetic natural gas as claimed in claim 14; it is characterized in that; 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, the throughput ratio that can regulate fresh synthesis gas in the first via pipeline and the second road pipeline by first variable valve and second variable valve.
16. the adiabatic methanation device of producing synthetic natural gas as claimed in claim 14 is characterized in that, described supercharging circulation device is recycle compressor or boosting jet pump.
17. the adiabatic methanation device of producing synthetic natural gas as claimed in claim 14, it is characterized in that, the described methanation refining plant that is arranged between methanation device and the methanation heat recovery steam-making device comprises an isothermal methanation reactor and the 3rd heat reclamation device, one way outlet of second heat reclamation device connects the inlet of isothermal methanation reactor, the outlet of isothermal methanation reactor connects the inlet of the 3rd heat reclamation device, and the outlet of the 3rd heat reclamation device connects methanation heat recovery steam-making device.
18. the adiabatic methanation device of producing synthetic natural gas as claimed in claim 14, it is characterized in that, the described methanation refining plant that is arranged between methanation device and the methanation heat recovery steam-making device comprises the 3rd adiabatic methanation reactor, the 4th adiabatic methanation reactor, the 3rd heat reclamation device, the 4th heat reclamation device, one way outlet of second heat reclamation device connects the inlet of the 3rd adiabatic methanation reactor, the outlet of the 3rd adiabatic methanation reactor connects the inlet of the 3rd heat reclamation device, the outlet of the 3rd heat reclamation device connects the inlet of the 4th adiabatic methanation reactor, the outlet of the 4th adiabatic methanation reactor connects the inlet of the 4th heat reclamation device, and the outlet of the 4th heat reclamation device connects methanation heat recovery steam-making device.
19. the adiabatic methanation device of producing synthetic natural gas as claimed in claim 14, it is characterized in that, the described methanation refining plant that is arranged in the methanation heat recovery steam-making device comprises the 3rd adiabatic methanation reactor and the 3rd heat reclamation device, and this methanation heat recovery steam-making device comprises the 4th heat reclamation device, first gas-liquid separator, second recycle compressor, heat exchanger, second gas-liquid separator, moisture eliminator, the 3rd recycle compressor, one way outlet of second heat reclamation device connects the inlet of the 4th heat reclamation device, the outlet of the 4th heat reclamation device connects the inlet of first gas-liquid separator, the pneumatic outlet of first gas-liquid separator connects the inlet of second recycle compressor, the outlet of second recycle compressor connects the inlet of the 3rd adiabatic methanation reactor by heat exchanger, the outlet of the 3rd adiabatic methanation reactor is by connecing the inlet of the 3rd heat reclamation device by heat exchanger, the outlet of the 3rd heat reclamation device connects the inlet of second gas-liquid separator, the pneumatic outlet of second gas-liquid separator connects the inlet of moisture eliminator, the outlet of moisture eliminator connects the SNG pipe network, the liquid exit of the liquid exit of first gas-liquid separator and second gas-liquid separator connects the inlet of phlegma treatment unit simultaneously, and the outlet of phlegma treatment unit connects boiler.
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