CN103496667B - The treatment process of hydrogen product is prepared in a kind of methanol synthetic discharged gas delayed recovery also part - Google Patents
The treatment process of hydrogen product is prepared in a kind of methanol synthetic discharged gas delayed recovery also part Download PDFInfo
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- CN103496667B CN103496667B CN201310491249.2A CN201310491249A CN103496667B CN 103496667 B CN103496667 B CN 103496667B CN 201310491249 A CN201310491249 A CN 201310491249A CN 103496667 B CN103496667 B CN 103496667B
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Abstract
The invention provides a kind of methanol synthetic discharged gas delayed recovery and the treatment process of part preparation hydrogen product, methanol synthetic discharged gas delayed first through first paragraph membrane separation, the infiltration gas preparing amounts of hydrogen enough from a large amount of off-gas enters PSA, and first paragraph membrane sepn infiltration gas obtains highly purified hydrogen through purifying further; Remaining most of off-gas continues to enter second segment membrane sepn as impermeable gas, and infiltration gas returns synthesis unit as hydrogen rich gas, recycle; The stripping gas of second segment membrane sepn impermeable gas and PSA sends battery limit (BL) as fuel gas.Novelty of the present invention PSA and two section membrane sepn is carried out organic assembling, in more reasonable, economic mode, realize reclaim methanol synthetic discharged gas delayed while, prepared again a certain amount of high-purity hydrogen; Be particularly useful for reclaiming extensive coal chemical engineering equipment methanol synthetic discharged gas delayed and prepare the situation of a small amount of high-purity hydrogen simultaneously.
Description
Technical field
The invention belongs to technical field of coal chemical industry, particularly relate to a kind of methanol synthetic discharged gas delayed recovery and the treatment process of part preparation hydrogen product.
Background technology
In the methanol synthesizer of Coal Chemical Engineering Project, in order to prevent the accumulation of rare gas element, usually a small part circulation gas can be discharged after reactor.This part gas, because hydrogen content is higher, if directly burning will cause the serious waste of valuable gases.For this reason, the Normal practice of current methanol synthesizer is the membrane separation technique adopting investment lower, utilize the infiltration difference of gas molecule in film, filter out macromolecular components in off-gas, by hydrogen upgrading in off-gas, return methanol synthesizer, recycle, remaining impermeable gas then sends battery limit (BL) (or processing further) as fuel gas.Disclosed in patent 10185209B a kind of conformity membrane be separated, conversion, decarburization technique, reached farthest reclaim methanol synthetic discharged gas delayed in the method for active principle.Off-gas is after membrane separation, and infiltration gas returns methanol-fueled CLC; Impermeable gas does not use as fuel gas, but further by conversion process, the CO in impermeable gas is converted into H2, and through decarburization, finally adopts membrane sepn by after decarbonization gas concentrate, return methanol-fueled CLC.
Along with the large of Modern Coal-based Chemical project, the scale of methanol synthesizer also increases increasingly, and the tolerance of corresponding off-gas also increases gradually.Simultaneously, along with Coal Chemical Industry product is by the further extension of methyl alcohol to alkene, the design concept that full factory plans as a whole is increasingly thorough, and higher methanol synthetic discharged gas delayed while realization is reclaimed of hydrogen concentration, there has also been new purposes: for a certain amount of highly purified hydrogen prepared by downstream olefin and poly-unit.The method being prepared hydrogen by synthesis purge gas of current report, all for all preparing hydrogen by methanol synthetic discharged gas delayed, both only by the mode of one section of membrane sepn serial connection PSA, and report be there is no for the treatment process also partly preparing hydrogen product while methanol synthetic discharged gas delayed recovery.In producing synthesis gas from coal coproduction carbon monoxide, methyl alcohol, hydrogen, the integrating device refining synthetic gas and method disclosed in patent 102191086A, the off-gas of methanol-fueled CLC is after membrane sepn concentrate density of hydrogen, all enter PSA to purify, prepare the high-purity hydrogen of 99.9% or allocate with other hydrogen.Do not address in its method while how realizing methanol synthetic discharged gas delayed recovery and also partly prepare hydrogen product.Even if take the traditional method that this only one section of membrane sepn is connected in series with PSA, while going to realize methanol synthetic discharged gas delayed recovery and part preparation hydrogen product function, also seeming, shortcoming is more, investment and energy consumption all higher, reason is as follows:
Membrane sepn infiltration air circuit serial connection PSA(is see accompanying drawing 1), as the membrane sepn serial connection PSA technique that patent 102191086A mentions.For the situation of part preparation hydrogen product while methanol synthetic discharged gas delayed recovery, infiltration gas only part enters PSA, and remainder returns methanol-fueled CLC.Because in infiltration gas, density of hydrogen is higher, the scale of this kind of situation PSA device is more reasonable; But in order to the pressure ensureing per-meate side can meet the requirement that PSA prepares elevated pressures hydrogen product, the pressure drop of membrane sepn both sides must control at lower level, ensureing that, under the prerequisite that hydrogen retrieval rate is desirable, the quantity of required film increases, and the investment of film separating system is increased.
For membrane sepn impermeable gas loop serial connection PSA(see accompanying drawing 2), now membrane sepn is not subject to the restriction of pressure needed for hydrogen product, and scale is more reasonable; But be impermeable gas due to what enter PSA, density of hydrogen is very low, and PSA needs to be processed large-minded, and PSA's is larger, invests higher; Meanwhile, for reaching desirable hydrogen retrieval rate, desorption pressures is lower, and gas desorption quantity is large, needs to be equipped with compressor and compresses, can meet the pressure requirements of fuel gas pipe network.
Summary of the invention
For realizing methanol synthetic discharged gas delayed recovery and the object of part preparation hydrogen product, overcome the defect of traditional technology, the present invention proposes a kind of methanol synthetic discharged gas delayed recovery and the treatment process of part preparation hydrogen product.By novelty, PSA and two section membrane sepn is carried out organic assembling, by appropriate design, effectively by two Systematical control in Reasonable Scale, in more reasonable, economic mode, while realization recovery is methanol synthetic discharged gas delayed, prepare again a certain amount of high-purity hydrogen; Be particularly useful for reclaiming extensive coal chemical engineering equipment methanol synthetic discharged gas delayed and prepare the situation of a small amount of high-purity hydrogen, the investment of whole treatment unit and working cost are all lower simultaneously.
Technical scheme of the present invention is as follows:
The treatment process that hydrogen product is also partly prepared in a kind of methanol synthetic discharged gas delayed recovery combines with two sections of membrane sepn and pressure-variable adsorption (PSA), and while realizing methanol synthetic discharged gas delayed recovery, also part prepares hydrogen product, and idiographic flow is as follows:
Off-gas from methanol-fueled CLC first all enters first paragraph membrane sepn, and prepare appropriate infiltration gas according to subject hydrogen product volume, now most of off-gas is still in impermeable gas;
The infiltration gas of first paragraph membrane sepn enters PSA device, the higher and pressure of preparation purity and infiltration gas close hydrogen product concentration ~ 99.9% of the hydrogen (or higher); Stripping gas sends battery limit (BL) as fuel gas;
The impermeable gas of first paragraph membrane sepn continues to enter second segment membrane sepn, and the infiltration gas (concentration ~ 85% of hydrogen) after concentrate returns upstream methanol synthesis unit, recycles effective gas wherein; Second segment membrane sepn infiltration gas, after decompression, sends battery limit (BL) as fuel gas.
In above-mentioned technique, methanol synthetic discharged gas delayed only part is for the preparation of hydrogen product, and subject hydrogen product volume only accounts for a part for methanol synthetic discharged gas delayed middle hydrogen total amount, is about 1/7 ~ 1/10 or smaller scale;
In above-mentioned technique, when first paragraph membrane separation, owing to only preparing required small amount infiltration gas from relatively large off-gas, the requirement of this process to first paragraph membrane sepn is lower, only need minority 1 ~ 5 film (fixed depending on tolerance), the infiltration gas of density of hydrogen higher (~ 90%) can be prepared.Simultaneously, because the rate of recovery of this step to hydrogen is less demanding, therefore the film both sides of one section of membrane sepn are when economical rationality, lower pressure drop is maintained than being easier to, ensure that the infiltration gas entering downstream PSA device has higher pressure, the high-purity hydrogen product that pressure is higher can be prepared.
In above-mentioned technique, second segment membrane sepn needs recover hydrogen as far as possible, and second segment film needs 5 ~ 20 films (fixed depending on tolerance); Because first paragraph membrane sepn only isolates a small amount of hydrogen from off-gas, the density of hydrogen therefore entered in the impermeable gas of second segment membrane sepn is still in higher level; Meanwhile, because impermeable gas still has the elevated pressures with off-gas similar level, therefore, relative to conventional process scheme, in the present invention, two-segment film separation requirement is not significantly increased.
In above-mentioned technique, stripping gas is by simple compression or do not compress and namely can be used as fuel gas and send battery limit (BL); Because the density of hydrogen in first paragraph membrane sepn infiltration gas is higher, therefore lower to the requirement of the PSA device of downstream serial connection, the scale of PSA device is less, relative to conventional processes, greatly reduces investment outlay.Simultaneously, because in unstripped gas, density of hydrogen is higher, therefore when preparing product hydrogen, the desorption process of pressure-variable adsorption can operate at elevated pressures, stripping gas is made to have higher desorption pressures, therefore, only need a little supercharging or directly discharge the requirement that can meet fuel gas pressure in project.
The beneficial effect that the present invention has:
The present invention makes full use of the technical characterstic of membrane sepn and PSA, by innovation two sections of membrane sepn and PSA combine, realize methanol synthetic discharged gas delayed recovery and the object of part preparation hydrogen product, efficiently solve Problems existing when traditional technology is applied in this field, greatly reduce investment and the working cost of device, make Technology reasonable more economically, based on above technical characterstic, advantage of the present invention can be summarized as follows:
1, off-gas is through one section of membrane sepn, and pressure drop is lower, ensure that final hydrogen product has higher pressure,
Increase the scope of application of hydrogen product;
2, the requirement of membranous system is not increased, ensure that whole treatment process has lower investment, there is good economic benefit;
3, the unstripped gas density of hydrogen entering PSA device is higher, and PSA device can according to subject hydrogen product custom-made by size, and unit scale is less, invests lower;
4, the unstripped gas density of hydrogen entering PSA device is higher, and PSA desorption process can maintain elevated pressures, and stripping gas pressure is high, and required stripping gas compressor is less, and working cost is lower.
Accompanying drawing explanation
Fig. 1 is that traditional PSA is serially connected in membrane sepn infiltration air circuit process flow diagram.
Fig. 2 is that traditional PSA is serially connected in membrane sepn impermeable gas loop process schematic flow sheet.
Fig. 3 is present invention process schematic flow sheet.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but do not limit the present invention.
The technique means realized for making the present invention, creation characteristic and effect easy to understand, also give further instruction to content of the present invention by reference to the accompanying drawings below by application example.
Following instance is for certain olefin hydrocarbon making by coal synthesizing engineering plastic project, and the scale of methanol device is about 1,500,000 tons/year of methyl alcohol, methanol synthetic discharged gas delayed (6.52MPaG, H
2~ 68.2%) amount is about 24700Nm
3/ h, downstream needs amounts of hydrogen to be 3100Nm
3/ h(pressure 4.0MPaG, H2 ~ 99.9%).
Technical process is described as follows:
Methanol synthetic discharged gas delayedly first enter first paragraph membrane sepn, obtained 3690Nm
3/ h(4.4MPaG, H
2~ 91.3%) infiltration gas, sends into PSA device, remaining impermeable gas 21010Nm
3/ h(6.42MPaG, H
2~ 63.8%) second segment membrane sepn is entered.
First paragraph membrane sepn infiltration gas is purified through PSA device, obtained required product hydrogen 3101.68Nm
3/ h(pressure 4.0MPaG, H
2~ 99.9%).Stripping gas 588.32Nm3/h(~ 0.5MPaG) directly send battery limit (BL) as fuel gas.
First paragraph membrane sepn impermeable gas enters second segment membrane sepn, obtained 10736Nm3/h(3.37MPaG, H
2~ 90%) infiltration gas returns methanol synthesizer, recycles hydrogen wherein; Impermeable gas 10273Nm3/h, after decompression, sends battery limit (BL) as fuel gas.
In this project implementation process, the economic comparison of present invention process and traditional treatment process sees the following form:
By the contrast of upper table, in lifted example, the gross investment of present invention process is about 1,400 ten thousand yuan, and the gross investment that traditional PSA is serially connected in membrane sepn infiltration air circuit is about 2,800 ten thousand yuan, and the gross investment that traditional PSA is serially connected in membrane sepn impermeable gas loop is about 1,600 ten thousand yuan; Show that investment cost of the present invention saves greatly;
In addition, because present invention process stripping gas compressor year power consumption expense is zero, therefore after the running of several years, the working cost of present invention process also has very large advantage.
Above embodiments of the invention have been described in detail, but described content being only preferred embodiment of the present invention, can not being considered to for limiting practical range of the present invention.All equalizations done according to the present patent application scope change and improve, and all should still belong within patent covering scope of the present invention.
Claims (2)
1. a methanol synthetic discharged gas delayed recovery the treatment process of part preparation hydrogen product, it is characterized in that: this technique be with two sections of membrane sepn and pressure-variable adsorption (PSA) combined, while realization recovery is methanol synthetic discharged gas delayed, and part prepares high-purity hydrogen, be applicable to reclaiming extensive coal chemical engineering equipment methanol synthetic discharged gas delayed and prepare the situation of a small amount of high-purity hydrogen, idiographic flow is as follows simultaneously:
First off-gas from methanol-fueled CLC enters first paragraph membrane sepn, and the infiltration gas of first paragraph membrane sepn enters PSA device and prepares highly purified hydrogen; The impermeable gas of first paragraph membrane sepn enters second segment membrane sepn, obtains infiltration gas hydrogen rich gas and returns methanol synthesis unit circulation; Impermeable gas and PSA resolution gas are sent battery limit (BL) and are made fuel gas or process further;
Methanol synthetic discharged gas delayed only part is for the preparation of hydrogen product;
First first paragraph membrane sepn processes off-gas, and prepare a certain amount of infiltration gas according to subject hydrogen amount, most of off-gas is still in impermeable gas; First paragraph film needs 1 ~ 5 film;
Second segment membrane sepn needs to reclaim the hydrogen in first paragraph membrane sepn impermeable gas as far as possible, and second segment film needs 5 ~ 20 films.
2. methanol synthetic discharged gas delayed recovery according to claim 1 the treatment process of part preparation hydrogen product: described resolution gas is by simple compression or do not compress and namely can be used as fuel gas and send battery limit (BL).
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| CN105460891B (en) * | 2014-09-03 | 2017-11-07 | 中国石油天然气股份有限公司 | Recycling method and system of methanol purge gas |
| US10774273B2 (en) | 2017-07-31 | 2020-09-15 | Uop Llc | Process and apparatus for recovering hydrogen from residue hydroprocessing |
| CN111348623B (en) * | 2020-03-30 | 2023-11-07 | 广西精典化工新材料有限公司 | Hydrogen recovery and purification system in 'methanol oxidation to formaldehyde' purge tail gas |
| CN114751379B (en) * | 2022-03-31 | 2023-12-15 | 国家能源集团宁夏煤业有限责任公司 | Method for preparing hydrogen by separating and synthesizing tail gas |
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| CN102191086A (en) * | 2010-03-16 | 2011-09-21 | 河南省化工设计院有限公司 | Integrated integration device and method for coproducing carbon monoxide, methanol, hydrogen and refined synthetic gas in process of producing synthetic gas from coal |
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