CN1069687C - Process for purification to obtain high-purity synthetic gas by adsorption - Google Patents
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Abstract
The present invention relates to a method for producing synthetic gas, which is characterized in that the purification technology of an adsorption method with a high product gas recovery rate is used for replacing the technologies of methanation, dewatering, drying and cryogenic purification, and an adsorption purifying unit is regenerated to obtain CH4-enriched end gas to be recycled. Thereby, the circular conversion of methane in the end gas is realized, and the raw material consumption in the process of steam conversion is furthest reduced. Simultaneously, high-quality hydrogen gas or high-quality synthetic gas can be obtained.
Description
The invention belongs to the method for hydro carbons gas making, say more specifically, being hydro carbons transforms and adsorption cleaning is produced the method for the synthetic gas that hydrogen or synthetic ammonia uses through water vapor.
Hydro carbons transforms the gas that makes through water vapor, is mainly used in synthetic ammonia, hydrogen manufacturing, synthesizing methanol, oxo process etc.When this method was used to make synthetic ammonia, the raw material of employing comprised hydrocarbon gas (as Sweet natural gas, oil field gas), liquefied petroleum gas (LPG), lighter hydrocarbons (as petroleum naphtha), and its main flow process comprises: refining → steam reforming → CO conversion of raw material → take off CO
2→ methanation → compression, drying → ammonia synthetic (Dalian Polytechnic College is compiled, " Large Scale Synthetic Ammonia Plants synthetic gas production technique (hydrocarbon steam conversion method) ", Chemical Industry Press, in November, 1984 first version).Water vapor reforming hydrogen manufacturing method has: Foster, Wheeler method water vapor reforming hydrogen manufacturing (FWC), ICI Imperial Chemical Industries water vapor conversion method hydrogen manufacturing (ICI), Top's rope water vapor reforming hydrogen manufacturing (Topsoe), main flow process is basic identical with ammonia synthesis process with used raw material, its main flow process: comprise feed purification → steam reforming → CO conversion → take off CO
2The hydrogen of the required purity of → methanation → obtain (Petroleum Association of Japan compiles, Research Institute of Petro-Chemical Engineering translates, " petroleum refining process method handbook ", petroleum industry press, in July, 1979 Beijing first version).Steam reforming hydrogen manufacturing and synthetic ammonia difference are that process for making hydrogen does not generally need the secondary reformer of atmospheric oxidation heat supply.
In recent years, along with raising up and the lighter hydrocarbons shortage of resources of energy prices, promoted energy-saving and cost-reducing development and application for the novel process of purpose and new technology, various energy-saving steam conversion process arise at the historic moment, the energy-saving technology of the most representative C.F.Braun, its main processes: a section of desulfurization of raw material → 695 ℃ is gentle to be transformed, two sections conversion → high and low temperature shift → solvent methods of excess air take off CO
2→ methanation → molecular sieve drying → cryogenic purification → compression → ammonia synthesis (Yu Zunhong etc. are write, " large-scale ammonia plant process analysis " Sinopec press).This flow process can low gentleness transform owing to increased the cryogenic purification technology, reduces the thermal load of process steam consumption and one-stage converter significantly; After fresh synthesis gas drying and cryogenic purification are handled, amount of inert gas reduces, and oxycarbide and moisture are trace, help to improve the utilization ratio of ammonia net value and fresh synthesis gas, reduce the quantity discharged of speeding to exit, can reduce the power consumption of recycle gas compressor and ice maker simultaneously; This technical process also increases the handiness and the reliability of production operation.But still there are weakness such as the big and process air compressor power consumption of raw material consumption amount is big in this technology.
In recent years,, in hydrogen manufacturing and ammonia synthesis process, use transformation absorption (PSA) technology, take off CO to replace traditional solvent method in order to obtain highly purified hydrogen or hydrogen nitrogen synthetic gas
2And methanation.This worker's process comprises that desulfurization of raw material → steam reforming → CO conversion → PSA purifies → obtain high-purity hydrogen.But because the PSA hydrogen recovery rate is lower, a large amount of hydrogen enter PSA tail gas, thereby the corresponding raw material consumption amount that strengthened.(chief editor such as Xiang Dehui, " chemical fertilizer catalyst application manual ", Chemical Industry Press).
The objective of the invention is to overcome the deficiency of prior art, propose a kind of hydrocarbon steam conversion method that can reduce raw material, fuel, steam and power consumption and can obtain high-quality synthetic gas or hydrogen.
Realize purpose main technical schemes of the present invention: with the adsorption and purification technology of a kind of improved high hydrogen, the hydrogen and nitrogen gas rate of recovery replace existing technology methanation, dehydrate or methanation, dehydrate, the cryogenic purification process, and the rich CH that the adsorption cleaning regeneration unit is obtained
4Tail gas recycles, and realizes that the circulation of methane in the tail gas transforms.
Realize another kind of technical scheme of the present invention: the pressure swing adsorption process (VPSA) with transformation absorption (PSA) or vacuum regeneration takes off CO
2And adsorption method for purifying (takes off CO, CH
4, CO
2, H
2Deng) the solvent method that replaces in the prior art of combination process take off CO
2, methanation, drying and cryogenic purification technology, the rich CH that adsorption cleaning regeneration unit process obtains
4Tail gas recycles.
The concrete technical process of preparation synthetic ammonia of the present invention may further comprise the steps:
1. feed purification: according to a conventional method lightweight material is carried out hydroconversion reactions under the effect of catalyzer, the hydrogen sulfide of generation again with reactive desulfurizing agent, the total sulfur in the unstripped gas is reduced to below the 0.2ppm;
2. steam reforming: select to comprise pre-inversion, one section conversions, two sections conversion, heat exchange type conversion, autothermal conversion process can be combined a kind of, two or more conversion process, as required with the acquisition best effect;
3.CO conversion: be selected from one or both flow processs that combine in known high temperature shift, middle temperature transformation, the low temperature shift, when adopting high temperature shift and low temperature shift serial flow, the CO in (2) step in the reforming gas generates CO with steam reaction under catalyst action
2And H
2, make the CO in the conversion gas reduce to 0.1-0.5%;
4. take off CO
2: can adopt common solvent absorption or adopt absorption method to comprise the pressure swing adsorption process (VPSA) of pressure swing adsorption process (PSA), vacuum regeneration, make the CO in the gas
2Content is reduced to below 1%, preferably below 0.5%;
5. methanation: the CO and the CO that remove the remnants in (4) step gas
2, make CO and CO in the methanation gas
2Sum is reduced to about 10ppm;
6. adsorption method for purifying: enter from the gas in (5) step adsorbers a kind of, two or more sorbent materials are housed, adsorption bed is optionally adsorbed easy absorbed component and is comprised CH
4, CO
2, H
2O, difficult absorbed component comprises H
2, N
2, Ar discharges by adsorber product end, the methane-rich gas that bed regeneration obtains is recycled to (1) step feed purification or (2) step steam reforming unit, or as the one-stage converter fuel of steam reforming part;
7. compression is synthetic: the gas behind the adsorption cleaning enters ammonia synthesis system after compression.
Above-mentioned (5) ground beetle alkanisation gas can earlier compressedly enter (6) step adsorber again, and tail gas recycles after compression or directly.
Above-mentioned (5) ground beetle alkylation process can be saved, and (4) step is taken off CO
2Gas after compression or not compressed (6) step adsorption method for purifying unit that directly enters earlier, this moment, must to increase the CO that comprises molecular sieve adsorbent bed in the adsorption method for purifying unit, with highly selective adsorbing and removing CO, guarantees to obtain high-quality gas.
When one section conversion and two sections conversion serial flows are adopted in steam reforming of the present invention, because methane-rich gas recycles, can adopt relatively mild operational condition, methane content is 0.1-3% in the reforming gas of secondary reformer outlet, preferably 0.5-1%; Because allow higher remaining methane, it is 2.3-4.5 that conversion process can adopt lower steam/hydrocarbons ratio, preferably 2.7-3.5; Secondary reformer needn't add excessive air, only need satisfy the desired hydrogen nitrogen of ammonia synthesis operation than getting final product.One-stage converter adopts common temperature out 750-850 ℃, preferably 780-820 ℃; Secondary reformer adopts lower temperature out 850-1000 ℃, preferably 880-950 ℃.
CO converter unit of the present invention can adopt the high temperature shift flow process as required, and the CO in the conversion gas is reduced to about 3%, also can adopt the middle temperature transformation flow process, and the CO in the conversion gas is reduced to about 1%.
Adsorption method for purifying technology of the present invention, at USP3176444,3986849,3430418, sorbent material and Technology that 2944627 PSA that propose use can adopt, described sorbent material comprises molecular sieve, gac, silica gel, activated alumina, can select wherein a kind of, composite bed that two or more sorbent materials are formed according to different applicable cases such as raw material composition, pressure, treatment capacity etc.Generally at normal temperatures through absorption and the working cycle of depressurization desorption regenerated of boosting, detailed process comprises at least two adsorbers of the present invention, each adsorber:
(1) absorption: raw material constantly enters adsorber under higher adsorptive pressure, and difficult adsorbed components is discharged from the product end of adsorber by adsorption bed;
(2) forward pressure release: after adsorption process finishes, adsorption bed is decompressed to an intermediate pressure, the difficult absorbed component that retains in the dead space in the adsorption bed is constantly discharged from the product end of adsorber, so pressure leak process is referred to as forward pressure release, the pressure leak process expellant gas can be used for the boost gas or the sweeping gas of another adsorption bed;
(3) reverse pressure release: after forward pressure release finishes, adsorption bed begins to be decompressed to lower desorption pressures, is adsorbed an adsorbed components and constantly discharges from the adsorber feed end, so pressure leak process is called reverse pressure release, the easy absorbed component of separating sucking-off enters the tail gas buffering system, recycles;
(4) purge: the adsorption bed after the reverse pressure release, under desorption pressures, forward difficult adsorbed gas or other difficult adsorbed gas of pressure leak process discharge purge adsorption bed with another adsorption bed, to reduce the dividing potential drop of easy absorbed component in the adsorption bed, adsorption bed is further regenerated, can also adopt heating and blowing gas or the method that vacuumizes realizes the desorb of bed;
(5) boost: the adsorption bed behind the desorption and regeneration is under the lower pressure, by with difficult absorbed component (forward pressure release expellant gas and product gas) its pressure being risen to higher adsorptive pressure.So far, above-mentioned adsorption bed has been finished boost an absorption and a depressurization desorption regenerated process.
It is worthy of note that above-mentioned easy absorbed component and difficult absorbed component can be one-components, also can be the mixture of two or more gaseous fractions.Obviously, all pressures number of times that above-mentioned adsorption cleaning unit is adopted, whether the body storage tank of all calming the anger is set, whether sweeping gas storage tank etc. is set is optimized selection according to different concrete application scenarios (as unstripped gas composition, pressure, treatment capacity etc.), to reach best economical effectiveness.
The compression process of unitary gas compression processes of of the present invention entering (6) step or methane-rich gas should be compressed to (1) step feed purification or the required pressure of (2) step steam reforming.
The present invention also can be used for hydrogen manufacturing, and its technology and ammonia synthesis process flow process are basic identical, comprising: former
Methanation unit in the said process can save equally.
Methanation gas can compress earlier and enter the adsorption cleaning unit again in the above-mentioned flow process, and tail gas recycles after compression or directly.
Described steam reforming also can transform for pre-inversion, one section conversion, two sections conversions, heat exchange types, one or more combination process in the autothermal conversion process, usually producing hydrogen from steam conversion technology does not adopt two sections conversion process, as adopt two sections conversion process, want aerating oxygen or oxygen enrichment (rather than air) to secondary reformer usually; When adopting one section to transform, one-stage converter is being operated than under the severe condition usually, and to realize high transformation efficiency and low remaining methane content, the one-stage converter temperature out is 780-920 ℃, and preferably 820-880 ℃, steam/hydrocarbons ratio 2.3-5.5, preferably 2.7-4.5.
Major advantage of the present invention and effect:
The present invention is owing to adopt adsorption cleaning, and tail gas recycles, so the steam reforming rate of raw material is near 100%, to reduce consumption of raw materials to greatest extent; The present invention can adopt lower steam/hydrocarbons ratio and one section gentle conversion, thereby reduces the thermal load of one-stage converter greatly, reduces the fuel consumption of one-stage converter effectively; Under the prerequisite that improves raw material availability, realize that the gentleness of secondary reformer transforms, need in secondary reformer, not add excess air, thereby reduce the power of process air compressor significantly; The present invention can obtain high-quality synthetic gas or hydrogen, helps to reduce the energy expenditure of hypomere operation, reduces the quantity discharged of speeding to exit of lower procedure; The present invention is because the adsorption cleaning unit can allow impurity (CH in the unstripped gas
4, CO, CO
2) content fluctuation, so CO in the methane in the reforming gas, conversion gas and the CO in the adsorption tower gas
2When content raises, can not influence the quality of hydrogen or hydrogen nitrogen synthetic gas, not influence the normal running of lower procedure yet, thereby strengthen the reliability and the handiness of operation; Owing to can allow to absorb the CO in the overhead gas
2Content is higher, thereby reduces the steam of carbon rejection process and the consumption of power.
Below by FB(flow block) characteristics of the present invention are described;
Fig. 1 is typical synthetic ammonia process figure;
Fig. 2 takes off CO for typical solvent method
2The hydrogen manufacturing flow process;
Fig. 3-Fig. 5 is synthetic ammonia process figure of the present invention;
Fig. 6-Fig. 7 is a hydrogen manufacturing schema of the present invention;
By shown in Figure 1, typical synthetic ammonia process comprises that feed purification 1, steam-reforming 2, CO conversion 3, carbon dioxide removal 4, methanation 5, compression 6, drying 7, synthetic 8 operations namely obtain synthetic ammonia, and I is that raw material, II are that water vapour, III are that air, IV are synthetic ammonia among the figure.
By shown in Figure 2, solvent method takes off CO2Hydrogen making technological process, basic similar to Fig. 1 flow process, just can obtain required hydrogen V by methanation is later.
By Fig. 3-shown in Figure 5, synthetic ammonia process figure of the present invention has increased adsorption cleaning unit 9, and regeneration tail gas is that circulating air VI recycles, and the difference of Fig. 3 and Fig. 4 is: Fig. 3 is that methanation gas directly enters adsorption cleaning unit 9, and regeneration obtains is rich in CH4Tail gas VI after compression direct circulation uses, and Fig. 4 is that methanation gas compresses first and enters adsorption cleaning unit 9 again, and tail gas after compression (figure does not mark) or direct circulation uses; Fig. 5 and Fig. 3, Fig. 4 difference are that carbon dioxide removal 4 gases directly enter adsorption cleaning unit 9 without methanation, tail gas VI recycles after compression, also carbon dioxide removal 4 gases can be entered adsorption cleaning unit 9 after compression, regeneration tail gas VI after compression or direct circulation use (figure does not mark)
Fig. 6 and shown in Figure 7, the main difference point of Hydrogen making technological process of the present invention and Fig. 2 is to increase adsorption cleaning unit 9, make hydrogen, regeneration tail gas VI can be recycled, the difference of Fig. 6 and Fig. 7 is that Fig. 6 is that methanation 5 gases can obtain hydrogen behind adsorption cleaning unit 9, and regeneration tail gas VI recycles after compression, also can be that methanation 5 gases compress first and enter adsorption cleaning unit 9 again, regeneration tail gas VI after compression or direct circulation use (figure does not mark); Fig. 7 is that carbon dioxide removal 4 gases directly enter adsorption cleaning unit 9 without methanation, and regeneration tail gas VI recycles after compression, also can be to take off CO2Gas compresses first and enters adsorption cleaning unit 9 again, regeneration tail gas VI after compression or direct circulation use (figure does not mark).
Further set forth characteristics of the present invention below by example.
Example 1
This example is to be raw material with the Sweet natural gas, adopts ammonia synthesis process shown in Figure 3:
Desulfurization of raw material, one section steam reforming, two sections steam reformings, high temperature CO conversion, low temperature CO conversion, solvent methods take off CO
2, methanation, adsorption method for purifying, tail gas compression cycle, its main processes operational condition and leading indicator see Table 1, and compare with the described ammonia flow process of typically closing of Fig. 1.Described adsorption method for purifying unit adopts ten adsorbers, each adsorber pack into successively aluminum oxide, silica gel and molecular sieve.
As shown in Table 1, raw material total conversion rate of the present invention reaches 99.6%, and the unit consumption of fuel of raw material is all low than known typical process.
Example 2
This example is to make raw material with petroleum naphtha, and adopt Fig. 6 process for making hydrogen flow process: feed purification, one section steam reforming, high temperature CO conversion, solvent method take off CO
2, adsorption method for purifying, tail gas compression cycle, concrete operations condition and the key technical indexes see Table 2, and compare with the hydrogen producing technology of the known PSA method of purification simultaneously.
Table 1
| Project | Typical process | Example 1 |
| Desulfurization temperature, ℃ | 370 | 370 |
| One section transforms temperature out, ℃ | 822 | 800 |
| Two sections transform temperature out, ℃ | 1003 | 955 |
| Steam/hydrocarbons ratio, mol/mol | 3.5 | 3.0 |
| The high temperature shift temperature out, ℃ | 431 | 432 |
| The low temperature shift temperature out, ℃ | 254 | 227 |
| Synthetic gas pressure, Mpa | 2.5 | 2.5 |
| The adsorption cleaning unit hydrogen rate of recovery, % | 95 | |
| Methane content in two sections reforming gas, mol% | 0.32 | 0.51 |
| CO content in the low temperature shift gas, mol% | 0.49 | 0.40 |
| Absorb CO in the overhead gas 2Content, mol% | 0.1 | 0.12 |
| Raw material consumption kg/1000Nm 3Pure hydrogen | 237 | 225 |
| Unit consumption of fuel ＂ | 144 | 119 |
| The total conversion rate of raw material, % | 95.6 | 99.6 |
| Synthetic gas is formed, mol% | ||
| H 2 | 73.74 | 74.67 |
| N 2 | 24.58 | 24.92 |
| CH 4 | 1.1 | 0.1 |
| H 2O | 0.27 | Do not have |
| CO+CO 2 | ＜10PPm | ＜5PPm |
| Ar | 0.31 | 0.31 |
| Methane-rich gas pressure, Mpa | 0.03 | |
| Methane-rich gas is formed, mol% | ||
| H 2 | 59.24 | |
| N 2 | 19.74 | |
| CH 4 | 19.70 | |
| CO+CO 2 | -50ppm | |
| H 2O | 1.07 | |
| Ar | 0.25 |
Table 2
| Project | Typical case's prior art | Example 2 of the present invention |
| The feed purification temperature, ℃ | 360 | 360 |
| One section transforms temperature out, ℃ | 820 | 820 |
| Steam/hydrocarbons ratio, mol/mol | 3.5 | 3.5 |
| The high temperature shift temperature out, ℃ | 412 | 417 |
| The product hydrogen pressure, Mpa | 2.4 | 2.4 |
| The adsorption cleaning unit hydrogen rate of recovery, % | 93 | |
| The PSA purified hydrogen rate of recovery, % | 90 | |
| CH in the reforming gas 4, content, mol% | 6.3 | 6.6 |
| CO content in the hypermutation gas, mol% | 2.3 | 2.97 |
| Absorb CO in the overhead gas 2Content, mol% | 0.17 | |
| Raw material consumption, kg/1000Nm 3Pure hydrogen | 314 | 202 |
| Unit consumption of fuel, kg/1000Nm 3Pure hydrogen | 39* | 145 |
| Product hydrogen is formed mol% | ||
| H 2 | ≥99.99 | ≥99.99 |
| CH 4 | ＜0.01 | ＜0.01 |
| CO+CO 2 | ≤20PPm | ≤20PPm |
| Methane-rich gas pressure, Mpa | 0.03 | |
| Methane-rich gas is formed, mol% | ||
| H 2 | 34.14 | |
| CH 4 | 42.60 | |
| CO | 21.47 | |
| CO 2 | 0.70 | |
| H 2O | 1.09 |
* the prior art fuel consumption only is outer afterburning material consumption, does not comprise self-produced PSA cleaning of off-gas, and this tail gas is as the fuel of one-stage converter.
Claims (5)
1. hydrocarbon steam conversion method, the concrete steps of producing hydrogen or hydrogen nitrogen synthetic gas comprise:
(1) feed purification: it is refining that raw material carries out the desulfurization detoxification in the presence of hydrogenation catalyst, sweetening agent, and the total sulfur in the unstripped gas is reduced to below the 0.2ppm;
(2) steam reforming: be selected from that pre-inversion, one section conversion, two sections conversions, heat exchange types transform, the combination of a kind of, two or more conversion process in the autothermal;
(3) CO conversion: be selected from one or both flow processs that combine in high temperature shift, middle temperature transformation, the low temperature shift, when adopting high temperature shift and low temperature shift serial flow, the CO in the conversion gas reduces to 0.1-0.5%;
(4) take off CO
2: adopt solvent adsorption method or absorption process to comprise pressure swing adsorption process, vacuum pressure swing adsorption process in the conversion gas in (3) step, make the CO in the gas
2Content is reduced to below 1%;
(5) methanation: the CO that removes the remnants in (4) step gas
2And CO, its total amount is reduced to about 10ppm;
It is characterized in that:
(6) adsorption method for purifying: hydrogen or hydrogen nitrogen synthetic gas from (5) step directly or after compression enter adsorbers a kind of, two or more sorbent materials are housed, and optionally adsorb easy absorbed component and comprise CH
4, CO
2, H
2O, difficult absorbed component comprises H
2, N
2, Ar discharges by adsorber product end, the methane-rich gas that bed regeneration obtains after compression or direct cycle to (1) step feed purification or (2) steam reforming unit, or as the unitary one-stage converter fuel of steam reforming.
2. in accordance with the method for claim 1, it is characterized in that (4) step takes off CO
2Gas is without (5) ground beetle alkanisation unit, directly or enter (6) step adsorption method for purifying unit after the compression.
3. in accordance with the method for claim 1, it is characterized in that the described sorbent material in (6) step adsorption method for purifying unit comprises molecular sieve, gac, silica gel, activated alumina.
4. in accordance with the method for claim 2, it is characterized in that taking off CO without (5) ground beetle alkanisation unitary (4) step
2Gas directly enters (6) step during the adsorption method for purifying unit, and it is adsorbent bed to increase the CO that comprises molecular sieve in (6) step unit.
5. in accordance with the method for claim 1, it is characterized in that (6) go on foot the adsorption method for purifying unit and are made up of at least two adsorbers, each adsorber passes through the working cycle of boost absorption and depressurization desorption at normal temperatures.
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| FR2857884B1 (en) * | 2003-07-24 | 2006-11-24 | Air Liquide | PROCESS FOR PRODUCTION OF HYDROGEN BY ADSORPTION AND INSTALLATION FOR CARRYING OUT SAID METHOD |
| CN101373839B (en) * | 2007-08-20 | 2010-07-07 | 北京科技大学 | Method and apparatus for removing CO, electrification method and system for fuel battery with proton exchange film |
| CN102001624B (en) * | 2010-11-22 | 2012-09-05 | 神华集团有限责任公司 | Method for producing hydrogen by using hydrocarbonaceous material gas |
| CN103509609A (en) * | 2013-09-29 | 2014-01-15 | 天脊煤化工集团股份有限公司 | Gas purification process method combining suck-up purification and adsorption purification |
| CN103881765B (en) * | 2014-03-24 | 2015-07-08 | 中石化宁波工程有限公司 | Split circulating CO transformation process |
| CN105255531B (en) * | 2015-10-19 | 2018-07-06 | 中国华能集团清洁能源技术研究院有限公司 | A kind of system and method for low temperature distillation coal gas preparing natural gas parallel connection hydrogen producing |
| CN109748242B (en) * | 2017-11-03 | 2022-09-16 | 中国科学院大连化学物理研究所 | Adsorbent for efficient purification of hydrogen |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1069708A (en) * | 1991-08-24 | 1993-03-10 | 化学工业部西南化工研究院 | From ammonia factory conversion gas, remove the pressure swing adsorption technique of carbonic acid gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1069708A (en) * | 1991-08-24 | 1993-03-10 | 化学工业部西南化工研究院 | From ammonia factory conversion gas, remove the pressure swing adsorption technique of carbonic acid gas |
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