CN1660733A - Technique method for preparing synthesis gas of methyl by using transformation of hydrocarbons and water vapour - Google Patents
Technique method for preparing synthesis gas of methyl by using transformation of hydrocarbons and water vapour Download PDFInfo
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- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 46
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 230000015572 biosynthetic process Effects 0.000 title claims description 71
- 238000003786 synthesis reaction Methods 0.000 title claims description 71
- 238000000034 method Methods 0.000 title claims description 50
- 230000009466 transformation Effects 0.000 title description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 title 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 211
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims description 203
- 238000010926 purge Methods 0.000 claims description 41
- 230000008569 process Effects 0.000 claims description 38
- 238000011084 recovery Methods 0.000 claims description 31
- 239000001301 oxygen Substances 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 15
- 239000003546 flue gas Substances 0.000 claims description 15
- 239000000446 fuel Substances 0.000 claims description 14
- 238000002407 reforming Methods 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 10
- 239000002737 fuel gas Substances 0.000 claims description 7
- 230000005855 radiation Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 230000001502 supplementing effect Effects 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 3
- 238000000629 steam reforming Methods 0.000 claims description 3
- 230000000153 supplemental effect Effects 0.000 claims description 2
- 238000006057 reforming reaction Methods 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 39
- 230000001105 regulatory effect Effects 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 34
- 239000003345 natural gas Substances 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 238000005265 energy consumption Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 208000032170 Congenital Abnormalities Diseases 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
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- Hydrogen, Water And Hydrids (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for preparing the synthetic methanol gas from gas-state hydrocarbon and water vapor includes such steps as stage-one conversion, adding CO2 and O2, stage-two conversion, and regulating H2/C ratio to obtain high-temp synthetic metanol gas.
Description
Technical Field
The invention relates to a process method for preparing methanol synthesis gas, in particular to a process method which adopts a two-stage conversion method and is suitable for converting gaseous hydrocarbon to prepare the methanol synthesis gas.
Background
The method for preparing methanol by using gaseous hydrocarbon as a raw material comprises the working procedures of raw material gas compression, purification, conversion, synthesis gas and circulating gas compression, methanol synthesis, crude methanol rectification and the like. Methanol is a high energy consumption product, and the conversion (or called gas making) process is also a key process for synthesizing the methanol. The natural gas consumption in the conversion process accounts for the total energy consumption of the methanol synthesis process, the consumption of small and medium-sized devices is about 80%, and the consumption of large-sized devices is more than 90%. Therefore, the improvement of methanol production technologyfocuses on the aspects of adopting low energy consumption process, fully recovering and reasonably utilizing energy and single series large-scale of the device.
In the past, the methanol synthesis gas production technology taking natural gas as a raw material mostly adopts a traditional process of pressurizing natural gas steam and converting at one section. The main characteristics of said process are short flow, low investment, no consumption of oxygen, no need of matched air separation equipment, and its greatest defect is high energy consumption. The main reason for the high energy consumption is that H2unreasonable/C ratio: synthesis of methanol (CH)3OH) theory H2and/C is 2, and the total reaction formula for preparing methanol by using the gaseous hydrocarbon steam reforming method is as follows: that is, 1mol of CH4 is consumed per 1mol of CH4When OH, 1mol of H is left2，H2and/C is 3. The deficiency of hydrogen and carbon is the congenital defect of the process, and each ton of methanol has surplus H2Up to 700Nm3The above. Surplus of H2Accumulated in the purge gasThe purge gas amount of the methanol per ton can reach 1200Nm3The above. Part of the purge gas is returned to the primary reformer to be used as fuel gas, and the redundant purge gas is either externally supplied to be used as fuel gas or is burnt by a torch. Another reason is that: residual CH4High, one-stage conversion cannot guarantee CH4Conversion depth of (2), residual CH in general synthesis gas43-5 percent, directly causes high consumption of synthetic gas of unit product and large amount of synthetic cycle gas and purge gas, thereby causing high consumption of raw material and fuel natural gas and large amount of kinetic energy.
Because of the disadvantages of theabove-mentioned process, a two-stage reforming process with oxygen addition in a two-stage reformer has been developed.By using two-stage conversion, oxygen is reacted with CH in a two-stage furnace4Partial oxidation is carried out, and not only is heat released for CH4Deep conversion is carried out to lead residual CH in the synthesis gas4Content is less than or equal to 0.5 percent, and CH4CO formed by oxidation2Introducing into the synthesis gas to make the f value of the synthesis gas
Close to 2.0-2.1, better meets the synthesis conditions, greatly reduces the synthesis gas consumption, the synthesis circulation gas quantity and the purge gas quantity of unit products, greatly improves the alcohol content and the alcohol net value of the outlet gas of the synthesis tower, reduces the natural gas consumption by 80-100Nm in the traditional process of converting one pressurized section of methanol per ton3。
And the technology of preparing the synthesis gas by heat exchange type conversion is applied to the transformation of small and medium-sized methanol devices, and an LCM (liquid crystal module) process, namely a heat exchange type pure oxygen two-stage conversion process, is developed. The process uses the heat exchange type primary reformer to replace an external heating type primary reformer, most of the fuel natural gas occupying about 1/4 of the total consumption of the natural gas is saved, and the consumption of the methanol natural gas per ton is reduced to 886Nm3And the energy consumption of the small and medium-sized devices reaches the energy consumption level of the large-sized devices. The heat exchange type conversion gas making technology is a great breakthrough of the synthesis gas making technology; the heat exchange type pure oxygen two-stage conversion process is the most advanced new process for producing methanol synthetic gas in the world today. The LCM process has been used in a new 5.4 million ton/year methanol plant in australia, but no large scale industrial practice has been available.
On the basis of the above process, a heat exchange type pure oxygen two-stage conversion process similar to the LCM process is developed.
The common characteristic of the pure oxygen two-stage conversion process and the heat exchange type pure oxygen two-stage conversion process is that the inert gas (CH) in the methanol synthesis gas is solved by adding oxygen in the two-stage converter4) The high content and the serious imbalance of H-C cause the synthetic gas consumption, the circulation gas quantity and the purge gas quantity of a unit product to be greatly reduced, thereby reducing the consumption of raw material hydrocarbon and power. Compared with the traditional process of primary steam conversion, the method has the advantages that the cost of adding a secondary reformer and an air separation device is increased (the heat exchange type pure oxygen secondary conversion process also uses the heat exchange type primary reformer to replace an external heating type primary reformer), the purpose of reducing the consumption of raw material, fuel hydrocarbon and power is achieved, and the method is an energy-saving process for synthesizing the methanol.
The energy-saving process still has the defects, and is mainly characterized in that:
the total amount of purge gas remains large and is extremely uneconomical for use as a fuel, according to the synthesis reaction formula:
due to H2CO is consumed in a ratio of 2: 1, H2、CO2Is consumed in a ratio of 3: 1, so that the f-number in the synthesis loop is
Much greater than 2. In addition, H in the synthesis column inlet gas2The excessive amount of the catalyst is beneficial to the reaction of synthesizing methanol, reduces side reaction and lightens H2S poisoning and reduced carbonyl iron formation are also advantageous. Thus, different methanol synthesis processes require feeding H in the column gas2Excess, f value
Generally controlled between 2.5 and 6, so as to synthesize H in the purge gas2The content is as high as 65-85%, and the purge gas amount of ton methanol still reaches 800Nm3. The larger the production scale, the greater the total amount of purge gas. The above processMethod of reducing the height H2The purge gas content is used as fuel, and CH is wasted4Conversion to H2Heat energy consumed and pressure H2The kinetic energy consumed is therefore extremely uneconomical. Purging CO from the gas2Not only is wasted, but also is discharged into the atmosphere to cause environmental pollution.
Synthesis gas H2The strength of the/C regulation is limited by the heat balance of the conversion process. Although after the secondary reformer is oxygenated, CH4CO formed by oxidation2Into the synthesis gas to make the synthesis gas H2C tends to be reasonable, but CH4Oxidation to CO2The reaction of (a) is a strongly exothermic reaction, the heat of reaction is with the second-stage furnace CH4Balancing the heat consumed by the deep conversion of the water vapor, otherwise, adjusting the conversion load distribution of the primary and secondary converters to achieve the heat balance of the conversion system. The above process adjusts H as limited by the heat balance of the conversion process2the/C approach is not flexible enough and the adjustment force is limited.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a process method for preparing methanol synthesis gas by converting hydrocarbons and water vapor, which can reduce the consumption of raw material natural gas and oxygen and flexibly adjust the H of the synthesis gas2The ratio of/C, thereby improving the synthesis production efficiency and alcohol net value and realizing yield increase and energy saving.
The invention is realized by the following technical scheme:
a process for preparing methanol synthesis gas by reforming hydrocarbons and water vapor comprises the following steps:
feeding the mixed gas of gaseous hydrocarbon and water vapor as raw material into a primary reformer, and carrying out the conversion reaction of the gaseous hydrocarbon and the water vapor in the primary reformer;
the outlet gas temperature of the primary reforming furnace is 650-4The content is 2-35%, and CO is supplemented in the primary converted gas2Adding oxygen, feeding into a secondary converter, and performing deep conversion reaction of gaseous hydrocarbon and water vapor in the secondary converterShould, and by adjusting the CO added2And O2Amount of (2) adjusting H of secondary reforming off-gas2the/C ratio is that the reformed gas output from the secondary reformer is methanol synthesis gas; wherein, the heat required by the conversion reaction of the gaseous hydrocarbon and the water vapor in the first conversion furnace is provided by the mixed fuel gas of the gaseous hydrocarbon of the fuel burned by the burner and the exhaust gas of the purge gas recovery device in a radiation mode.
The temperature of the high-temperature reformed gas output from the secondary reformer, namely the methanol synthesis gas, is 800-4The content is 1-0.2%, the methanol synthesis gas recovers heat and byproduct steam through a heat exchanger, and after cooling, the methanol synthesis gas is added with H-rich gas sent by a purge gas recovery device2And (3) pressurizing the gas by a synthesis gas compressor, then sending the pressurized gas into a methanol synthesis system, and sending the prepared crude methanol into a rectification system for rectification to obtain the finished product methanol. Wherein, in the synthesis gas at the outlet of the synthesis gas compressor
Wherein, in order to ensure the smooth proceeding of the first-stage conversion reaction, the raw material gaseous hydrocarbon and the water vapor which are sent into the first-stage conversion furnace are pressurized to make the pressure of 1.0-6.0MPa, and after preheating, the temperature after preheating is 350-680 ℃.
Said supplemental CO in the primary reformed gas2For CO from flue gas recovery units2Gas and CO-rich gas sent from purge gas recovery device2A gas mixture of gases; wherein CO is supplemented2The position of (2) can be supplemented in the inlet of the secondary reformer, and can also be supplemented in the raw material gaseous hydrocarbon.
After the purge gas generated by the methanol synthesis system is treated by the purge gas recovery device, the product gas is divided into three types: rich in H2Gas, exhaust gas, rich CO2Gas, wherein the separated H-rich2Feeding the gas into an inlet of a synthesis gas compressor, and returning the gas to a methanol synthesis system; mixing the exhaust gas with fuel gaseous hydrocarbon, and feeding the mixture into a primary reformer to be used as fuel gas; rich in CO2Gas and CO from flue gas recovery2The gas is mixed and then used as the carbon supplementing gas of the secondary reformer.
In summary, the present invention has the following features: supplying CO to raw gaseous hydrocarbon or primary reformed gas2The consumption of raw natural gas and the consumption of oxygen can be reduced at the same time. Natural gas steam CO supplement2Transformation for preparing nailThe overall reaction formula for the alcohol is as follows:
compared with the total reaction formula for preparing the methanol by the steam reforming of the natural gas, 1/4mol of CO is added when each 1mol of the methanol is produced2The consumption of 1/4mol of raw material natural gas can be reduced, and simultaneously, the pure oxygen adding amount of a secondary furnace can be reduced by 1/2 mol; recovering H from purge gas2When the product is used as raw material for synthesizing methanol, the yield of methanol can be increased, and the consumption of natural gas and power can be correspondingly reduced. According to the purge gas quantity of 650Nm per ton of methanol3H in the purge gas2Content 72% H2Recovery rate is 90%420Nm hydrogen can be recovered from ton of methanol3Adding CO additionally2140Nm30.2 ton of methanol can be prepared. Thus, H in the purge gas was recovered2The yield increasing and energy saving effects are very obvious; by addition of CO2Can flexibly adjust the H of the synthesis gas according to different stages of the use of the synthesis catalyst2The ratio of C to H is strictly controlled2the/C ratio is between 2.0 and 2.1, thereby improving the synthesis production efficiency and the alcohol net value.
Drawings
FIG. 1 is a schematic flow diagram of a process according to the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and specific examples.
Referring to fig. 1, which is a schematic flow chart of the process of the present invention, the process for preparing methanol synthesis gas by converting hydrocarbons and steam comprises the following steps:
preheating a mixture of gaseous hydrocarbon and water vapor at a certain pressure, then sending the mixture into a conversion pipe of the primary conversion furnace 1, absorbing heat released by combustion of mixed gas of fuel hydrocarbon outside the pipe and exhaust gas output by the purge gas recovery device 5 and air, carrying out conversion reaction of the gaseous hydrocarbon and the water vapor under the catalytic action of a catalyst in the pipe, and discharging the converted mixture out of the primary conversion furnace 1 after the conversion reaction is carried out to a certain degree;
the primary reformed gas is supplemented with CO supplied from a flue gas recovery unit 62Gas and CO-rich gas sent from purge gas recovery unit 52The gas mixture enters the secondary reformer 2, is fully mixed with oxygen sent by an air separation device in a mixer at the top of the secondary reformer 2 and then is sprayed out, and hydrogen and oxygen are generated in a top spaceThe gas flow passes through the catalyst bed layer from top to bottom, and the deep conversion reaction of the gaseous hydrocarbon and the water vapor is carried out under the adiabatic condition by the heat provided by the hydrogen-oxygen combustion and the catalytic action of the catalyst;
the high-temperature secondary reformed gas reaching the index of the deep conversion of the gaseous hydrocarbon is output from the secondary reformer 2, namely the methanol synthesis gas;
the methanol synthesis gas output from the secondary reformer 2 is subjected to heat recovery and byproduct steam recovery by a heat exchanger (not shown in figure 1), cooled and added with H-rich gas from a purge gas recovery device 52The gas is pressurized by a compressor 3 and then sent to a methanol synthesis system 4, and the prepared crude methanol is sent to a rectification system (not shown in figure 1) for rectification to obtain the finished product methanol.
In addition, gaseous hydrocarbon as fuel and the exhaust gas sent by the purge gas recovery device 5 are mixed and then enter the radiation section of the primary reformer 1, after the gaseous hydrocarbon and other combustible gas in the mixed gas are mixed with air through a special burner, the gaseous hydrocarbon and other combustible gas in the mixed gas are subjected to combustion reaction with oxygen in the air, the released heat is transferred to airflow in the reformer tube in a radiation mode, and then the flue gas enters the convection section from the radiation section.
After the heat of the high-temperature flue gas is recovered by a plurality of groups of process medium preheaters in the convection section, the high-temperature flue gas is pumped out from the primary reformer 1 by a draught fan (not shown in figure 1) and sent into a flue gas recovery device 6 to remove CO2And (5) discharging after air is released. CO removal2CO-rich gas output by the gas and purge gas recovery device 52Mixing the gas, pressurizing and feeding the mixture into a secondary reformer 2 to be used as carbon supplementing gas.
The purge gas from the methanol synthesis system 4 enters a purge gas recovery device 5, effective gas in the purge gas is separated by adopting pressure swing adsorption or a membrane, and the recovered gas is divided into three types: rich in H2Gas, exhaust gas and rich CO2Gas, wherein the separated H-rich2The gas is sent to an inlet of a synthesis gas compressor 3, and returns to a methanol synthesis system 4 after being pressurized; the exhaust gas which is decompressed and desorbed is mixed with gaseous hydrocarbon which is used as fuel and then is sent into a primary reformer 1 to be used as fuel; vacuum desorption of CO-rich gas2CO recovered by gas and flue gas recovery unit 62Mixing the gas, pressurizing and feeding the mixture into a secondary reformer 2 to be used as carbon supplementing gas.
It is specifically stated that the CO is supplemented2It can be used for supplementing primary reformed gas and gaseous hydrocarbon as raw material.
Example (b):
the refined desulfurized raw material with the flow rate of 224.4Kmol/h, the pressure of 2.1MPa and the temperature of 350 DEG CNatural gas (total C95%, CO)26 percent) of the mixed gas is mixed with water vapor with the flow rate of 736.6Kmol/h, the pressure of 2.3MPa and the temperature of 220 ℃, the mixed gas is sent into a convection section natural gas/water vapor mixed gas preheater of a primary reformer 1 to be preheated to 510 ℃, and then the preheated mixed gas enters a reformer tube of the primary reformer 1, the mixed fuel gas outside the tube absorbs the heat released by the combustion of the air, and CH is carried out under the catalytic action of a catalyst in the tube4The conversion reaction with water vapor is carried out, the pressure of the primary conversion gas from the primary converter 1 is 1.84MPa, the temperature is 785 ℃, and the residual CH is4The content is 4% (based on dry gas, the same applies below).
From flue gas CO2The flow rate of the recovery device 6 is 28.7Kmol/h, the pressure is 0.1MPa, and the temperature is 40 ℃ CO2Gas (CO)299.5%) and CO-rich gas from purge gas recovery unit 5 at a flow rate of 44.1Kmol/h, a pressure of 0.1MPa and a temperature of 40 deg.C2Gas (CO)268.6％、CO 19％、CH47.8％、H23.5 percent), pressurizing to 1.94MPa, and entering a convection section CO of a primary converter 12The preheater was preheated to 420 ℃.
Oxygen (O) having a flow rate of 50.2Kmol/h, a pressure of 1.94MPa and a temperature of 100 ℃ from an air separation plant299.5 percent) and mixed with water vapor with the flow rate of 36.7Kmol/h, the pressure of 2.3MPa and the temperature of 220 ℃, and then the mixture enters a convection section oxygen and water vapor mixed gas preheater of a primary reformer 1 to be preheated to 420 ℃.
The above primary reforming gas and CO2The mixed gas and the mixed gas of oxygen and water vapor simultaneously enter the secondary reformer 2, are fully mixed in the top mixer and then are sprayed out, firstly, the combustion reaction of hydrogen and oxygen occurs in the top combustion zone, then the gas flow passes through the catalyst bed layer from top to bottom, and CH is carried out under the adiabatic condition by the heat provided by the combustion of hydrogen and oxygen and the catalytic action of the catalyst4Deep conversion reaction with water vapor. The flow rate of the secondary reforming gas sent out from the secondary reformer 2 is 1494.1Kmol/h, the pressure is 1.78MPa, the temperature is 900 ℃, and the residual CH is4＜0.5％，
The secondary reformed gas output from the secondary reformer 2 is methanol synthesis gas, after the heat is recovered by a multistage heat exchanger recovery device, the water vapor condensate is separated and cooled to 40 ℃ by water, and the hydrogen-rich gas with the flow rate of 147Kmol/H from the purge gas recovery device 5 is mixed with the hydrogen-rich gas2Qi (H)299.5%) and mixed gas Then the mixture is pressurized to 5.4MPa by a compressor 3 and sent to a methanol synthesis system 4 for final preparationObtaining crude methanol 334.3Kmol/h (9518kg/h) which comprises CH as the main component3OH 72％、CO21.3％、H2And (3) O26.7%. Purge gas (H) having a flow rate of 212.6Kmol/H, a pressure of 4.8MPa and a temperature of 40 ℃ discharged from the methanol synthesis system 4274.4％、CO 6.7％、CO214.9％、CH42.1 percent) and sent to a PSA purge gas recovery unit 5.
Mixing fuel natural gas (total C95% and CO 26%) with the flow rate of 77.8Kmol/H with exhaust gas (H261.5%, CO 22.9%, CO 22.1% and CH 43.7%) with the flow rate of 22.7Kmol/H from a purge gas recovery device 5, sending the mixture into a radiation section of a primary reformer 1, mixing the mixture with air with the flowrate of 85mol/H through a special burner, carrying out combustion reaction on combustible gases such as CH4, H2 and CO in the mixture and oxygen in the air, transferring the released heat to airflow in a reformer tube in a radiation mode, and then transferring high-temperature flue gas (CO 898Kmol/H and the temperature of 750-29.5% of oxygen, O22%) from the radiant section into the convection section. After the heat of the high-temperature flue gas is recovered by a plurality of groups of process medium preheaters in the convection section, the temperature is reduced to 180 ℃, and the high-temperature flue gas is pumped out from the primary reformer 1 by an induced draft fan and sent into a flue gas recovery device 6.
Finally, it should be noted that: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; thus, while the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.
Claims (8)
1. A process for preparing methanol synthesis gas by converting hydrocarbons and water vapor is characterized by comprising the following steps: feeding gaseous hydrocarbon and steam as raw materials into a primary reformer, carrying out a reforming reaction of the gaseous hydrocarbon and the steam in the primary reformer, and supplementing CO into primary reformed gas output from the primary reformer2And oxygen is added and then sent into a secondary converter, the deep conversion reaction of gaseous hydrocarbon and water vapor is carried out in the secondary converter, and CO is added2、O2Amount of (b) to adjust the H of the secondary reforming off-gas2the/C ratio is that the reformed gas output from the secondary reformer is methanol synthesis gas; wherein the burners in the primary reformer burn a mixture of fuel gaseous hydrocarbons and the purge gas from the purge gas recovery unitThe fuel gas provides the heat required for the reforming reaction of the gaseous hydrocarbons and steam by radiation.
2. The process of claim 1, wherein the high temperature reformed gas from the secondary reformer, i.e. the methanol synthesis gas, is cooled by recovering heat and byproduct steam through a heat exchanger, and then the cooled reformed gas is fed into the purge gas recovery device to recover H-rich gas2And (3) pressurizing the gas by a synthesis gas compressor, then sending the pressurized gas into a methanol synthesis system, and sending the prepared crude methanol into a rectification system for rectification to obtain the finished product methanol.
3. The process for preparing methanol-containing syngas by reforming hydrocarbons with steam as claimed in claim 1, wherein the supplemental CO is added to the primary reformed gas2For CO supplied from flue gas recovery units2Gas and CO-rich gas sent from purge gas recovery device2A gas mixture of gases; wherein CO is supplemented2The position of (2) can be supplemented in the inlet of the secondary reformer, and can also be supplemented in the raw material gaseous hydrocarbon.
4. The process for preparing methanol synthesis gas by hydrocarbon and steam reforming as claimed in claim 2 or 3, wherein the purge gas recovery unit is used for treating the purge gas generated by the methanol synthesis system, and the treated product gas is divided into three types: rich in H2Gas, exhaust gas, rich CO2Gas, wherein H is enriched2Feeding the gas into an inlet of a synthesis gas compressor, and returning the gas to a methanol synthesis system; mixing the exhaust gas with fuel gaseous hydrocarbon, and feeding the mixture into a primary reformer to be used as fuel gas; rich in CO2Gas and CO from flue gas recovery2The gas is mixed and then used as the carbon supplementing gas of the secondary reformer.
5. The process for preparing methanol synthesis gas by reforming hydrocarbons with steam as claimed in claim 1, 2 or 3, wherein the pressure of the raw gaseous hydrocarbons and steam fed into the primary reformer is 1.0-6.0MPa, and after preheating, the raw gaseous hydrocarbons and steam are fed into the reformer tube of the primary reformer at a temperature of 350-680 ℃.
6. The process for preparing methanol synthesis gas by reforming hydrocarbons with steam as claimed in claim 1, 2 or 3, wherein the outlet gas temperature of the primary reformer is 650-4The content is 2-35%.
7. The process for preparing methanol synthesis gas by reforming hydrocarbons with steam as claimed in claim 1, 2 or 3, wherein the outlet gas temperature of the secondary reformer is 800-1000 ℃, and the CH in the secondary reforming is4The content is 0.2-1%,
8. the process for producing methanol synthesis gas by reforming hydrocarbons with steam as claimed in claim 2, wherein the synthesis gas is introduced into the synthesis gas at the inlet of the synthesis gas compressor
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014111310A1 (en) | 2013-01-17 | 2014-07-24 | Shell Internationale Research Maatschappij B.V. | Process for the preparation of synthesis gas |
| CN105347302A (en) * | 2015-08-28 | 2016-02-24 | 中国石油化工股份有限公司 | Method for producing synthesis gas by converting natural gas |
| CN106553995A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | Natural gas and carbon dioxide dry reforming process for preparing synthetic gas |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62108833A (en) * | 1985-11-05 | 1987-05-20 | Mitsubishi Heavy Ind Ltd | Production of feed gas for reactor |
| CN1057627A (en) * | 1991-08-08 | 1992-01-08 | 庞玉学 | Series conversion technology of hydrocarbon vapours |
| CN1218916C (en) * | 2000-09-04 | 2005-09-14 | 成都华西化工研究所 | Method for expanding production of methyl alcohol synthesis equipment by using natural gas as raw material |
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2004
- 2004-02-25 CN CNB2004100060028A patent/CN100425586C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014111310A1 (en) | 2013-01-17 | 2014-07-24 | Shell Internationale Research Maatschappij B.V. | Process for the preparation of synthesis gas |
| CN105347302A (en) * | 2015-08-28 | 2016-02-24 | 中国石油化工股份有限公司 | Method for producing synthesis gas by converting natural gas |
| CN106553995A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | Natural gas and carbon dioxide dry reforming process for preparing synthetic gas |
| CN106553995B (en) * | 2015-09-30 | 2019-05-28 | 中国石油化工股份有限公司 | Natural gas and carbon dioxide dry reforming process for preparing synthetic gas |
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| Publication number | Publication date |
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| CN100425586C (en) | 2008-10-15 |
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Assignee: CHENGDU GENERAL ENGINEERING TECHNOLOGY Co.,Ltd. Assignor: Pang Yuxue Contract record no.: 2011510000123 Denomination of invention: Technique method for preparing synthesis gas of methyl by using transformation of hydrocarbons and water vapour Granted publication date: 20081015 License type: Exclusive License Open date: 20050831 Record date: 20110810 |
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