CN101412932A - Sulfur-tolerant shift process for preparing methyl methanol syngas - Google Patents
Sulfur-tolerant shift process for preparing methyl methanol syngas Download PDFInfo
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Abstract
The invention provides a CO sulfur tolerant shift method for preparing methanol synthesis gas. The method at least comprises the following two stages of shift: crude gas is pretreated and is heated up to 180 to 260 DEG C, the gas enters a first reactor for the shift reaction when a water to gas volume ratio is 0.1 to 0.55, the bed temperature is 330 to 420 DEG C, and the CO volume content is 36 to 48 percent after the first shift reaction; and the gas from the first reactor is cooled down to 200 to 280 DEG C through heat exchange and water spray, the gas enters a second reactor for the shift reaction when a water to gas volume ratio is 0.1 to 0.75, the bed temperature is 390 to 450 DEG C, and the dry basis CO volume content in the final outputted gas is 8 to 35 percent. A CO sulfur tolerant shift catalyst is used during the two stages of shift. The outputted gas at the second stage can be directly used or for preparing the methanol synthesis gas or be used for preparing the methanol synthesis gas after a third stage of deep shift gas distribution. The method has the advantages of low water to gas ratio, energy conservation, low equipment cost, wide raw material sources, and the like.
Description
Technical field
The present invention relates to a kind of high concentration CO unstripped gas and produce the sulfur resistant conversion process of methyl methanol syngas, specifically relating to a kind of is the sulfur resistant conversion process that two sections of raw material high concentration CO unstripped gass or multistage are produced methyl methanol syngas with the coal.
Background technology
Methyl alcohol is a kind of important basic chemical raw materials, can be used for producing multiple organic productss such as formaldehyde, acetic acid, dimethyl terephthalate (DMT).Methyl alcohol also is important solvent, has been widely used in agricultural chemicals, medicine, spices and three big synthetic materials productions.Particularly after the eighties; because the Environment Protection Policy of gasoline " unleaded " is carried out by world industry developed country; make with methyl alcohol to be that the addition for leadless gasoline MTBE of raw material has obtained exploitation and a large amount of application; become the second largest methyl alcohol user who is only second to formaldehyde; the output and the consumption of methyl alcohol are all increased rapidly, become one of the world today's largeization product.
Entered since 21 century, owing to the influence that is subjected to be becoming tight petroleum resources day, the coal chemical industry of China has changed a Rapid development stage over to, and gasification system methyl alcohol the introduction and the traditional technology of novel process have occurred and improved the situation that starts at the same time.In numerous gasification system methyl alcohol novel procesies, the space flight coal gasification novel procesies such as (being called for short the HL gasification) of the coal gasification (being called for short Shell coal gasification and GSP gasification technology respectively) of Holland's shell and the exploitation of group company of Siemens, the strange coal gasification of transforming in Shandong (being called for short the BGL gasification) and China's independent development is subjected to the favor of China's chemical enterprise very much.Though these novel procesies have the advantage of its uniqueness, because of the CO content in the unstripped gas that makes up to more than 60%, not only increased the weight of the CO conversion load of sulfur-resisting transformation system, but also might cause that the methanation side reaction of high heat release makes the bed overtemperature.Therefore how segmentation, the control of primary reformer reaction depth and suppress problem such as methanation side reaction of shift conversion step just becomes the key that can high CO content process gas be successfully used to methanol production.
Patent ZL200610018566.2 discloses a kind of high-concentration carbon monoxide two-dimensional transform method, with CO volumetric concentration 〉=50%, sulphur content 〉=1 gram/rice
3Raw material preheating to 240 ± 20 ℃, arrived gas/vapour 0.9-1.1 by steam-laden, through one section of one-level or two sections wide temperature shifts of anti-sulphur, gas stops 1-2 second at Reaktionsofen, and reaction back CO volumetric concentration＜46.1% is again through two-stage two-segment or three sections sulphur resisting and low temp conversings, 180-260 ℃ of two-dimensional transform control furnace temperature, gas stops 2-2.5 second, and vapour/gas is 0.8-0.3, and reaction back CO volumetric concentration is 0.3-3%.This method has also increased energy consumption because the water vapour that vapour/gas than higher, needs is many.
Water/gas in the prior art in the CO conversion process is bigger, conversion for the high concentration CO unstripped gas, because CO concentration and water/gas are all high, the impellent of reaction is big, as long as the loading amount of one section catalyzer has a spot of variation, will obviously influence the hot(test)-spot temperature of bed, so catalyst consumption must be accurately, otherwise can cause the bad result of bed " temperature runaway " because reaction depth increases.Facts have proved the initial stage that some factory is driving, because of the load lower or because of the catalyst loading surplus bigger, overheating problem has appearred in first reactor, in order to reduce the temperature of reactor, water/gas is all brought up to more than 2.0, so not only causes the waste of energy, and moves owing to one section catalyzer is under Gao Shui/gas and the pyritous severe condition, it is frequent that catalyzer is changed, and influences ordinary production.For low-sulfur content factory in the unstripped gas, can the reversal of cure phenomenon appear because of high temperature and Gao Shui/gas also, and must select high sulphur coal for use or add sulphur or injection CS
2Increase the sulphur content in the process gas, just can keep ordinary production, limited the range of choice of feed coal.
Summary of the invention
The purpose of this invention is to provide a kind of high concentration CO unstripped gas more than two sections or two sections sulfur-resisting transformation prepare the technology of methyl methanol syngas.The consumption of the water vapour that this synthesis technique needs is few, reduced energy consumption, processing condition in shift converter relax, prolonged the work-ing life of catalyzer, simultaneously, the amount of sulphur in the unstripped gas is required low, the selection of having widened feed coal greatly, synthesising gas mixture directly or be used to prepare methyl alcohol after distribution.
For realizing that purpose of the present invention provides a kind of carbon monoxide sulfur-resisting transformation to prepare the method for synthesizing methanol synthetic gas, comprises first and second section conversion at least:
First section conversion: with the CO contents on dry basis is that the raw gas of 50-76% carries out pre-treatment, it is that 180-260 ℃, water/gas volume ratio enter first reactor during for 0.1-0.55 and carry out transformationreation that pretreated raw gas is heated to temperature, bed temperature is 330-420 ℃, and the volume content of CO is 36-48% after first transformationreation;
Second section conversion: the gas of the gas that comes out from first reactor and first reactor inlet carries out heat exchange, spray cooling enters second reactor to 200-280 ℃, water/gas volume ratio during for 0.1-0.75 and carries out transformationreation again, bed temperature is 390-450 ℃, and the volume content of butt CO is 8-35% in the last exit gas;
Use the CO sulfur-resistant transformation catalyst in above-mentioned first and second section conversion process.
The butt volume content of CO is 58-62% in the described raw gas.
Described pre-treatment comprises that raw gas enters the branch liquid/gas separator, and the raw gas that comes out from the separator top directly is heated, and the raw gas that perhaps comes out from the separator top adds water vapour or/and water spray adjustment water/gas volume ratio is heated later on.
Above-mentioned heated raw gas enters the detoxification groove again and sloughs impurity.
The mode of described heating comprises the exchange type heated air.
The gas of first reactor outlet is behind heat exchange, spray cooling, and water/gas volume ratio that interpolation water vapour is adjusted in the raw gas is 0.1-0.75.Water temperature during described the water spray is 25-100 ℃.
Described heat exchange comprises first reactor outlet gas and the mutual heat exchange of raw gas, and perhaps first reactor outlet gas and liquid heat exchange produce steam.Described liquid preferably water.
Described water spray comprises industrial water of condensation of spray or de-salted water.
Described de-salted water is meant removes or reduces to a certain degree water with the contained strong electrolyte that is easy to remove.
Unstripped gas from first reactor and small amount of steam (water/gas 0.1-0.55) are carried out CO and H under the effect of catalyzer
2The transformationreation of O, because transformationreation is thermopositive reaction, so the temperature of reactor outlet gas is higher, needs cooling just can proceed transformationreation, carrying out depth conversion in addition also needs to increase water/gas.The present invention earlier with the high-temperature gas of first reactor outlet through with first reactor inlet before gas carry out heat exchange and be reduced to certain temperature, and then the method for utilization water spray, it is further lowered the temperature reaches the temperature of subsequent conversion reaction and increases water/gas, be about to its heat recuperation like this and be used for the low gas of Heating temperature, replenished the moisture that gas that second reactor enters needs simultaneously, realized energy-conservation, fall can purpose.First reactor inlet has just added a large amount of steam (gas/vapour 0.8-1.1) in existing patent ZL200610018566.2, though also spray into the water for cooling humidification, and then enter interchanger and raw gas heat exchange, but can only replenish a spot of water/gas, well this part heat well not utilized.
The described preferred 0.21-0.3 of aqueous vapor volume ratio that enters the raw gas of first reactor inlet, more preferably 0.21-0.245.
By the aqueous vapor volume ratio in the CONTROL PROCESS gas, control the degree of depth of the first reactor transformationreation and the hot(test)-spot temperature of bed, be implemented under the prerequisite that the methanation side reaction does not take place, the high concentration CO unstripped gas is implemented conversion under the processing condition of low aqueous vapor volume ratio.Bed hot(test)-spot temperature and temperature in have very big relation in the reactor, and along with the increase of temperature in, the hot(test)-spot temperature of bed also increases, and the degree height of methanation side reaction is so the present invention's first shift converter temperature in preferably is controlled at 190-220 ℃.
Pressure in described first reactor is 3.0-6.5Mpa; The air speed of gas is 3000-8000h
-1
The butt volume content of CO is 36-48% in the gas that first reactor comes out.
Water in the described second section conversion/preferred 0.2-0.45 of gas volume ratio.
The bed hot(test)-spot temperature is 390-450 ℃ in described second reactor; The air speed of gas is 2000-6000h
-1
Butt of the present invention is that the dry gas with unit mass is that benchmark is represented gas property.
The content of CO is 8%-35% in the gas that comes out in second reactor, when the content of CO in second section reactor outlet gas is 18-22%, and the CO in the exit gas, H
2Between proportionlity meet the requirement for preparing methyl alcohol, the amount that does not need to allocate between them directly removes to prepare methyl alcohol.The content of CO is 8-17% in the gas that second reactor comes out, and needs to add suitable raw gas unstripped gas allotment, makes CO, H in its mixed gas
2Between ratio reach the preparation methyl alcohol requirement, perhaps enter the 3rd section reactor and carry out degree of depth CO conversion, afterwards again through distribution reach the preparation methyl alcohol requirement.When the content of CO is 23-35% in the gas that second reactor comes out, must carries out the 3rd section reactor and carry out degree of depth CO conversion.
The 3rd section conversion: the volume content of the CO that comes out from second reactor carries out heat exchange greater than 22% the gas and the gas of first reactor inlet, spray cooling enters the 3rd reactor to 190-260 ℃, water/gas volume ratio during for 0.2-0.3 and carries out transformationreation again, bed temperature is 320-410 ℃, the volume content of butt CO is 2-16% in the last exit gas, uses the CO sulfur-resistant transformation catalyst in described the 3rd section conversion process.
Described heat exchange comprises first or second reactor import and export gas and heat exchange mutually, and perhaps first or second reactor outlet gas and liquid heat exchange produce steam.
The 3rd section gas that comes out makes CO, H in its mixed gas through adding suitable raw gas unstripped gas allotment
2Between ratio reach the requirement of preparation methyl methanol syngas because also have the further purification of gas before synthetic entering methyl alcohol, even so the present invention pass through the activity that distribution also can not influence follow-up workshop section catalyst for methanol.
The gas of second and third reactor outlet or the gas after allotment adopt the method for the disclosed synthesizing methanol of prior art to prepare methyl alcohol.
In the prior art, usually improve water/gas ratio and suppress the methanation side reaction, the gas of the disclosed inlet mixture of patent ZL200610018566.2/vapour 0.9-1.1 for example, sometimes in addition vapour/gas ratio bring up to more than 2.0, so not only cause the waste of energy, and because one section catalyzer is under Gao Shui/gas and the pyritous severe condition and moves, it is frequent that catalyzer is changed, and influences ordinary production.Under low-sulfur content situation in the unstripped gas, can the reversal of cure phenomenon appear because of high temperature and Gao Shui/gas also, and must select high sulphur coal for use or add sulphur or injection CS
2Increase the sulphur content in the process gas, just can keep ordinary production, limited the range of choice of feed coal.
The water of first and second or three reactor inlets of the present invention/gas volume than be controlled at 0.1～0.55 respectively, in the 0.2-0.75,0.2-0.3 scope, the control of bed hot(test)-spot temperature is below 450 ℃, and adopt the QDB transformation catalyst, in conversion process, almost do not have the methanation side reaction to take place.Because water/gas of the present invention is starkly lower than prior art (water/gas 1.0), therefore adopt energy saving technology effect of the present invention remarkable.With a Methanol Plant of producing 300000 tons per year is example, can save 15 tons/h of steam at least, nearly 2,000 ten thousand yuan of year economic benefit.
The present invention can also change the low amounts of organic sulfur that has in the raw gas into H by when carrying out the CO conversion under these processing condition
2S makes in its sweetening process after conversion to be removed, and helps prolonging the life-span of methanol synthesis catalyst.
Compare with the technology of prior art for preparing methyl methanol syngas, for example, patent ZL88105383, patent ZL98120232.2, advantage such as it is relatively gentle that the present invention has processing condition, and the methanation side reaction takes place hardly, and the amount of the water vapour that needs is few.
The method of the synthetic gas of preparation methyl alcohol is changed in the anti-rheology of high concentration CO of the present invention, preferred version is: the CO contents on dry basis is that the raw gas of 50-76% at first enters gas-liquid separator, the raw gas that comes out from the separator top is heated to 180-260 ℃, after entering the detoxification groove and removing decon, enter first reactor and carry out transformationreation, the water of first reactor inlet wherein/gas volume ratio is 0.21-0.3, and air speed is 3000-8000h
-1Reaction pressure 3.0-6.5MPa, the volume content of butt CO is 36-48% in the first reactor outlet raw gas, second section conversion: the CO contents on dry basis be conversion gas and the gas that advances first reactor of 36-48% carry out heat exchange again spray cooling enter second reactor to 190-250 ℃ and carry out transformationreation, water/gas volume ratio is 0.2-0.45, temperature in is 390-450 ℃, and the hot(test)-spot temperature of second reactor bed is 390-450 ℃, and air speed is 2000-6000h
-1, the volume content of the second reactor outlet butt CO is 18-22%, uses the CO sulfur-resistant transformation catalyst in above-mentioned first and second section conversion process.
CO sulfur-resistant transformation catalyst described in first and second or the three sections conversion processes of the present invention is a cobalt molybdenum CO sulfur-resistant transformation catalyst.
The QDB series CO sulfur-resistant transformation catalysts of of the present invention first and second section or the three sections all preferred Qingdao of transformationreation connection letter chemical production were referring to " chemical fertilizer design " advertisement in 2006.
Described QDB catalyst series is meant with the magnesium-aluminium spinel to be that carrier, activeconstituents are CoO and MoO
3A class CO change catalyzer of anti-sulphur.
The QDB sulfur-resistant transformation catalyst that the present invention uses has Stability Analysis of Structures, higher intensity and anti-atomizing ability, higher low temperature active and lower performances such as light-off temperature.Even often fluctuation in operating process, the bed focus remains unchanged substantially; In allocating steam or hardening process into, the shift converter bed has minor amount of water to bring into unavoidably, makes the catalyzer efflorescence easily, and the QDB catalyzer has higher intensity and resistance to chalking energy.
The present invention prepares the methyl methanol syngas synthesis technique, and compared with prior art major advantage is as follows:
1, the present invention enters aqueous vapor volume ratio in each section reactor and inlet, bed temperature by control, makes that methanation side reaction degree is extremely low in the whole conversion process.
2, the industrialization cost is low
Save the consumption of steam, cut down the consumption of energy.Because the present invention's water/gas volume ratio in conversion process is starkly lower than the ratio of prior art, therefore adopt energy saving technology effect of the present invention remarkable; The first or second or the 3rd reactor outlet gas rationally utilizes its heat through processes such as heat exchange, water sprays, makes the energy consumption of whole technology reduce.
3, processing condition gentleness
Among the present invention first and second and or the water/gas of the 3rd reactor for lower, temperature in is below 260 ℃, the bed hot(test)-spot temperature is less than 450 ℃, processing condition obviously relax, the catalyzer of first and second or the 3rd reactor can be moved under the demulcent processing condition, reach the purpose in the work-ing life that prolongs catalyzer, industrial long-term operation is had important practical significance.
4, to H in the unstripped gas
2The S content requirement is low, the material choice wide ranges
Cobalt-molybdenum catalyst just can show high catalytic activity under sulfided state, and along with the H in the unstripped gas
2The also corresponding increase of the increase of S content, activity of such catalysts is therefore to the H in the unstripped gas
2The no maximum requirement in principle of S content.But owing to H in active constituent sulfide in the cobalt-molybdenum catalyst and the process gas
2There is the hydrolysising balance reaction between the S content, so under certain reaction temperature and water/gas condition, work as H
2Required minimum H when S concentration is lower than balance
2During S concentration, the reversal of cure phenomenon will occur and make catalyst deactivation, and temperature is high more, water/gas is big more, required H
2S concentration is also high more.When adopting existing three sections sulfur-resisting transformation Gao Shui/gas technology, required minimum H
2S is 1000ppm at least, and adopts low water/air-flow journey only to need H among the present invention
2S is that 300ppm can satisfy industrial requirement, has widened the range of choice of feed coal widely.
5, catalyzer can all domesticize
Therefore sulfur resistant conversion process of the present invention, can select the good and moderate domestic catalyst of low temperature active because temperature and vapour/gas are all low.Opening an auspicious Methanol Plant of producing 300000 tons per year with Henan is example, and can substitute the import catalyzer is 47m
3
Embodiment
Below be the specific embodiment of the present invention, described embodiment is in order to further describe the present invention, rather than restriction the present invention.
Embodiment 1
First section conversion: the CO contents on dry basis is that 62% raw gas at first enters gas-liquid separator, the raw gas that comes out from the separator top is heated to 205 ℃, after entering the detoxification groove and removing decon, enter first reactor and carry out transformationreation, the water of first reactor inlet wherein/gas volume ratio is 0.21, and temperature in is 205 ℃, and the hot(test)-spot temperature of first reactor bed is 378 ℃, reaction pressure 3.6MPa, the volume content of butt CO is 42% in the first reactor outlet raw gas;
Second section conversion: the CO contents on dry basis be 42% conversion gas with the inlet gas that advances first reactor carry out heat exchange again spray cooling to 210 ℃ enter second reactor and carry out transformationreation, water/gas volume ratio is 0.30, temperature in is 210 ℃, the hot(test)-spot temperature of second reactor bed is 405 ℃, the volume content of the second reactor outlet butt CO is 21%, satisfy the requirement of methanol production, QDB-04 type sulfur-resistant transformation catalyst is used in first and second section transformationreation.
Embodiment 2
First section conversion: the CO contents on dry basis is that 66% raw gas at first enters gas-liquid separator, the raw gas that comes out from the separator top adds steam and is heated to 200 ℃, after entering the detoxification groove and removing decon, enter first reactor and carry out transformationreation, the water of first reactor inlet wherein/gas volume ratio is 0.26, temperature in is 215 ℃, the hot(test)-spot temperature of first reactor bed is 400 ℃, reaction pressure 3.6MPa, the volume content of butt CO is 45% in the first reactor outlet raw gas;
Second section conversion: the CO contents on dry basis is 45% conversion gas and the gas that advances first reactor carries out heat exchange spray cooling to 260 ℃ again, feed water vapor again, enter second reactor and carry out transformationreation, water/gas volume ratio is 0.45, temperature in is 250 ℃, and the hot(test)-spot temperature of second reactor bed is 410 ℃, and the volume content of the second reactor outlet butt CO is 18%, QDB-04 type sulfur-resistant transformation catalyst is used in first and second section transformationreation, satisfies the requirement of methanol production.
Embodiment 3
First section conversion: the CO contents on dry basis is that 66% raw gas at first enters gas-liquid separator, the raw gas that comes out from the separator top adds steam and is heated to 200 ℃, after entering the detoxification groove and removing decon, enter first reactor and carry out transformationreation, the water of first reactor inlet wherein/gas volume ratio is 0.35, temperature in is 200 ℃, the hot(test)-spot temperature of first reactor bed is 428 ℃, reaction pressure 3.6MPa, the volume content of butt CO is 37% in the first reactor outlet raw gas;
Second section conversion: from one section gas that comes out with after 37% unstripped gas mixes, making the CO contents on dry basis is 45%, carry out heat exchange again spray cooling to 220 ℃ enter second shift-converter, water/gas volume ratio is 0.2, temperature in is 280 ℃, the hot(test)-spot temperature of second reactor bed is 410 ℃, and the volume content that makes the second reactor outlet butt CO is 19%, and QDB-03 type sulfur-resistant transformation catalyst is used in first and second section transformationreation.
Embodiment 4
First section conversion: the CO contents on dry basis is that 76% raw gas at first enters gas-liquid separator, the raw gas that comes out from the separator top adds steam and is heated to 180 ℃, after entering the detoxification groove and removing decon, enter first reactor and carry out transformationreation, the water of first reactor inlet wherein/gas volume ratio is 0.3, temperature in is 180 ℃, the hot(test)-spot temperature of first reactor bed is 420 ℃, reaction pressure 4.0MPa, the volume content of butt CO is 48% in the first reactor outlet raw gas;
Second section conversion: the CO contents on dry basis is that 48% conversion gas carries out heat exchange with the gas that advances first reactor and sprays water, adding water vapour, being cooled to 240 ℃ enters second reactor and carries out transformationreation, water/gas volume ratio is 0.62, temperature in is 240 ℃, the hot(test)-spot temperature of second reactor bed is 450 ℃, the volume content of the second reactor outlet butt CO is 10%, QDB-04 type sulfur-resistant transformation catalyst is used in first and second section transformationreation, satisfies the requirement of methanol production through the raw gas distribution.
Embodiment 5
First section conversion: the CO contents on dry basis is that 50% raw gas at first enters gas-liquid separator, the raw gas that comes out from the separator top is heated to 260 ℃, after entering the detoxification groove and removing decon, enter first reactor and carry out transformationreation, the water of first reactor inlet wherein/gas volume ratio is 0.55, and temperature in is 250 ℃, and the hot(test)-spot temperature of first reactor bed is 351 ℃, reaction pressure 6.5MPa, the volume content of butt CO is 36% in the first reactor outlet raw gas;
Second section conversion: the CO contents on dry basis be 36% conversion gas with the gas that advances first reactor carry out heat exchange again spray cooling to 230 ℃ enter second reactor and carry out transformationreation, water/gas volume ratio is 0.45, the hot(test)-spot temperature of second reactor bed is 412 ℃, the volume content 8% of the second reactor outlet butt CO, QDB-03 type sulfur-resistant transformation catalyst is used in first and second section transformationreation, satisfies the requirement of methanol production after the raw gas distribution.
Embodiment 6
First section conversion: the CO contents on dry basis is that 50% raw gas at first enters gas-liquid separator, the raw gas that comes out from the separator top adds steam and is heated to 240 ℃, after entering the detoxification groove and removing decon, enter first reactor and carry out transformationreation, the water of first reactor inlet wherein/gas volume ratio is 0.40, and temperature in is 240 ℃, and the hot(test)-spot temperature of first reactor bed is 360 ℃, reaction pressure 3.6MPa, air speed is 4000h
-1, the volume content of butt CO is 33% in the first reactor outlet raw gas;
Second section conversion: the CO contents on dry basis is that 33% conversion gas and the gas that advances first reactor carry out heat exchange spray cooling again, ℃ enter second reactor and carry out transformationreation adding steam to 220 then, water/gas volume ratio is 0.40, temperature in is 220 ℃, the hot(test)-spot temperature of second reactor bed is 407 ℃, the volume content of the second reactor outlet butt CO is 7.0%, satisfies the requirement of methanol production after the raw gas distribution.
Embodiment 7
First section conversion: the CO contents on dry basis is that 62% raw gas at first enters gas-liquid separator, the raw gas that comes out from the separator top adds steam and is heated to 200 ℃, after entering the detoxification groove and removing decon, enter first reactor and carry out transformationreation, the water of first reactor inlet wherein/gas volume ratio is 0.42, and temperature in is 215 ℃, and the hot(test)-spot temperature of first reactor bed is 400 ℃, reaction pressure 3.6MPa, air speed 8000h
-1, the volume content of butt CO is 42% in the first reactor outlet raw gas;
Second section conversion: the CO contents on dry basis be 42% conversion gas with the gas that advances first reactor carry out heat exchange again spray cooling to 220 ℃ enter second reactor and carry out transformationreation, water/gas volume ratio is 0.28, temperature in is 220 ℃, the hot(test)-spot temperature of first reactor bed is 410 ℃, and air speed is 4000h
-1, the volume content of the second reactor outlet butt CO is 20%, first and second section transformationreation uses QDB-03 type sulfur-resistant transformation catalyst to satisfy the requirement of methanol production.
Embodiment 8
First section conversion: the CO contents on dry basis is that 62% raw gas at first enters gas-liquid separator, the raw gas that comes out from the separator top adds steam and is heated to 200 ℃, after entering the detoxification groove and removing decon, enter first reactor and carry out transformationreation, the water of first reactor inlet wherein/gas volume ratio is 0.27, temperature in is 215 ℃, the hot(test)-spot temperature of first reactor bed is 360 ℃, reaction pressure 3.6MPa, the volume content of butt CO is 42% in the first reactor outlet raw gas;
Second section conversion: the CO contents on dry basis be 42% conversion gas with the gas that advances first reactor carry out heat exchange again spray cooling to 230 ℃ enter second reactor and carry out transformationreation, water/gas volume ratio is 0.17, the hot(test)-spot temperature of second reactor bed is 400 ℃, and the volume content of the second reactor outlet butt CO is 16%;
The 3rd section conversion: the CO contents on dry basis be 16% conversion gas with the gas that advances first reactor carry out heat exchange again spray cooling to 220 ℃ enter the 3rd reactor and carry out transformationreation, water/gas volume ratio is 0.25, the hot(test)-spot temperature of the 3rd reactor bed is 340 ℃, and the volume content of the 3rd reactor outlet butt CO is 3.6%; QDB-03 type sulfur-resistant transformation catalyst is used in first and second or three sections transformationreations, and last exit gas satisfies the requirement of methanol production after distribution.
Embodiment 9
First section CO conversion process parameter ginseng of this embodiment be embodiment 8, and other parameters are as follows:
Second section conversion: the CO contents on dry basis be 42% conversion gas with the gas that advances first reactor carry out heat exchange again spray cooling to 240 ℃ enter second reactor and carry out transformationreation, water/gas volume ratio is 0.28, the hot(test)-spot temperature of second reactor bed is 423 ℃, and the volume content of the second reactor outlet butt CO is 17%;
The 3rd section conversion: the CO contents on dry basis be 17% conversion gas with the gas that advances first reactor carry out heat exchange again spray cooling to 230 ℃ enter the 3rd reactor and carry out transformationreation, water/gas volume ratio is 0.21, the hot(test)-spot temperature of the 3rd reactor bed is 336 ℃, and the volume content of the 3rd reactor outlet butt CO is 3.5%;
QDB-02 type sulfur-resistant transformation catalyst is used in first and second or three sections transformationreations, and last exit gas satisfies the requirement of methanol production after distribution.
Embodiment 10
First and second of this embodiment section CO conversion process parameter reference example 8, other parameters are as follows:
The 3rd section conversion: the CO contents on dry basis be 30% conversion gas with the gas that advances first reactor carry out heat exchange again spray cooling enter the 3rd reactor for 200 ℃ and carry out transformationreation, water/gas volume ratio is 0.3, the hot(test)-spot temperature of the 3rd reactor bed is 347 ℃, and the volume content of the 3rd reactor outlet butt CO is 10%;
QDB-03 type sulfur-resistant transformation catalyst is used in first and second or three sections transformationreations, and last exit gas satisfies the requirement of methanol production after distribution.
Claims (9)
1, a kind of carbon monoxide sulfur-resisting transformation prepares the method for synthesizing methanol synthetic gas: comprise first and second section conversion at least:
First section conversion: with the CO contents on dry basis is that the raw gas of 50-76% carries out pre-treatment, it is that 180-260 ℃, water/gas volume ratio enter first reactor during for 0.1-0.55 and carry out transformationreation that pretreated raw gas is heated to temperature, bed temperature is 330-420 ℃, and the volume content of CO is 36-48% after first transformationreation;
Second section conversion: the gas of the gas that comes out from first reactor and first reactor inlet carries out heat exchange, spray cooling enters second reactor to 200-280 ℃, water/gas volume ratio during for 0.1-0.75 and carries out transformationreation again, bed temperature is 390-450 ℃, and the volume content of butt CO is 8-35% in the last exit gas;
Use the CO sulfur-resistant transformation catalyst in above-mentioned first and second section conversion process.
2, method according to claim 1 is characterized in that, the described water/gas volume ratio that enters the raw gas of first reactor inlet is 0.21-0.3.
3, method according to claim 1 is characterized in that, water/gas volume ratio is 0.2-0.45 in described second section conversion.
According to claim 1 or 3 described methods, it is characterized in that 4, described second section reactor comes out, and the CO volume ratio is 18-22% in the gas.
5, method according to claim 1 is characterized in that, the gas of described first reactor outlet adds steam or/and the mode of water spray increases water/gas volume ratio behind heat exchange, spray cooling.
6, technology according to claim 1, it is characterized in that, also comprise the 3rd section conversion, described the 3rd section is transformed to: the volume content of the CO that comes out from second reactor carries out heat exchange greater than 22% the gas and the gas of first reactor inlet, spray cooling enters the 3rd reactor to 190-260 ℃, water/gas volume ratio during for 0.2-0.3 and carries out transformationreation again, bed temperature is 300-410 ℃, the volume content of butt CO is 2-16% in the last exit gas, uses the CO sulfur-resistant transformation catalyst in described the 3rd section conversion process.
7, technology according to claim 1, it is characterized in that, the CO contents on dry basis is that the raw gas of 50-76% at first enters gas-liquid separator, the raw gas that comes out from the separator top is heated to 180-260 ℃, after entering the detoxification groove and removing decon, enter first reactor and carry out transformationreation, the water of first reactor inlet wherein/gas volume ratio is 0.21-0.3, and air speed is 3000-8000h
-1Reaction pressure 3.0-6.5MPa, the volume content of butt CO is 36-48% in the first reactor outlet raw gas, second section conversion: the CO contents on dry basis be conversion gas and the gas that advances first reactor of 36-48% carry out heat exchange again spray cooling enter second reactor to 190-260 ℃ and carry out transformationreation, water/gas volume ratio is 0.2-0.45, temperature in is 190-260 ℃, and the hot(test)-spot temperature of second reactor bed is 390-450 ℃, and air speed is 2000-6000h
-1, the volume content of the second reactor outlet butt CO is 18-22%, uses the CO sulfur-resistant transformation catalyst in above-mentioned first and second section conversion process.
According to each described method of claim 1-7, it is characterized in that 8, the butt volume content of CO is 58-62% in the described raw gas.
According to each described method of claim 1-8, it is characterized in that 9, described CO sulfur-resistant transformation catalyst is a cobalt molybdenum base sulfur-resistant transformation catalyst, preferred QDB type CO sulfur-resistant transformation catalyst.
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