CN104707453A - Two-stage catalytic hydrodesulfurization device - Google Patents
Two-stage catalytic hydrodesulfurization device Download PDFInfo
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- CN104707453A CN104707453A CN201510135149.5A CN201510135149A CN104707453A CN 104707453 A CN104707453 A CN 104707453A CN 201510135149 A CN201510135149 A CN 201510135149A CN 104707453 A CN104707453 A CN 104707453A
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Abstract
The invention relates to a two-stage catalytic hydrodesulfurization device; the two-stage catalytic hydrodesulfurization device can avoid inverse sulfuration reaction in a two-stage hydrogenation reactor; the two-stage catalytic hydrodesulfurization device comprises a pre-hydrogenation reactor, a first-stage hydrogenation reactor, a first-stage fine removing reactor, a second-stage hydrogenation reactor and a second-stage fine removing reactor sequentially connected in series; a pipeline is additionally arranged at the outlet of the pre-hydrogenation reactor, so that the outlet of the pre-hydrogenation reactor is directly connected to the inlet of the second-stage hydrogenation reactor; first-stage hydrogenation and second-stage hydrogenation are used in parallel or in series; a pipeline is additionally arranged at the outlet of the second-stage hydrogenation reactor, so that the outlet of the second-stage hydrogenation reactor is connected to the inlet of the first-stage fine removing reactor; and therefore, interchange use of the first-stage fine removing reactor and the second-stage fine removing reactor is realized. According to the two-stage catalytic hydrodesulfurization device disclosed by the invention, inverse sulfuration reaction in the event of carrying out second-stage hydrogenation is avoided; the hydrogenation catalytic processing capacity is improved; after being connected in parallel, first-stage hydrogenation and second-stage hydrogenation are spare to each other; normal production can be kept through another parallel reactor in the event of replacing a hydrogenation catalyst; and the process can be carried out without complete plant shutdown.
Description
Technical field
The present invention relates to the secondary catalyzing dehydrogen desulfurization of raw material such as chemicals such as coal (coke-stove gas) preparing natural gas, methyl alcohol etc.
Background technology
At present, in New Coal Chemical field, the fine desulfurizing technology flow process of unstripped gas such as chemicals such as coal (coke-stove gas) preparing natural gas, methyl alcohol etc. after thick desulfurization is generally: pre-hydrogenation, one-level hydrogenation, a fine de-sulfur, secondary hydrogenation, two fine de-sulfur (Fig. 1).Under normal circumstances by above-mentioned process operation, subsequent process can be reached requirement (below 0.1PPM) is removed to total sulfur content.Wherein the effect of one-level hydrogenation and secondary hydrogenation device is that hydrogenation reaction is occurred the organic sulfurs such as raw material cos wherein, mercaptan, thiophene under the effect of catalyst, generates inorganic hydrogen sulfide, to be removed in two-stage fine de-sulfur device.The hydrogenation reaction occurred in catalytic hydrogenation reaction device is as follows:
COS (cos)+H
2→ CO+H
2s
RSH(mercaptan)+H
2→ RH+H
2s
C
4h
4s (thiophene)+4H
2→ C
4h
10+ H
2s
The chemical reaction occurred in two-stage fine de-sulfur reactor is as follows:
Z
N0＋H
2S→Z
NS＋H
2O
If but due to reasons such as coking coal sulfur content are low, upstream wet desulfurization system desulfurized effect is good in actual production, the unstripped gas hydrogen sulfide index entering cleaning system, far below design load, makes the hydrogen sulfide content after one stage catalyzing hydrogenation reach or lower than the lower limit entering secondary catalytic hydrogenation reaction device.Now as gas enters secondary hydrogenation again, there is inverse sulphureting reaction by under the anaerobic environment in secondary hydrogenation reactor, add the hydrogen sulfide content entering subsequent process on the contrary.Desulfurication chemical reaction is as follows:
2CH
3
CHOHCOOH H
2
SO
4
→2CH
3
COOH 2CO
2
H
2
S
In this case, secondary hydrogenation device just cannot normally come into operation, and does not play due effect.Meanwhile, according to former technological process, one-level hydrogenation and secondary hydrogenation use because of series connection, must just can carry out by complete plant shutdown when changing one-level hydrogenation catalyst.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of secondary catalyzing dehydrogen desulfurization, and this device can be avoided, in secondary hydrogenation reactor, inverse sulphureting reaction occurs.
For solving above technical problem, the present invention improves on existing secondary catalyzing dehydrogen desulfurization basis.
A kind of secondary catalyzing dehydrogen desulfurization of the present invention, comprise pre-hydrogenator, one-level hydrogenation reactor, one-level essence dealkylation reaction device, secondary hydrogenation reactor and the secondary essence dealkylation reaction device of connecting successively, the outlet increase pipeline of described pre-hydrogenator directly connects the entrance of secondary hydrogenation reactor.After transformation, flow process is: the in parallel or series connection of pre-hydrogenation, one-level hydrogenation and secondary hydrogenation, a fine de-sulfur, two fine de-sulfur.Reach when the hydrogen sulfide content after one-level hydrogenation reaction or prescribe a time limit lower than entering the upper of secondary hydrogenation reactor, close the entrance of secondary hydrogenation reactor, unstripped gas only through one-level hydrogenation reactor and one-level essence dealkylation reaction device, doing so avoids in secondary hydrogenation reactor and inverse sulphureting reaction occurs after pre-hydrogenation.
As preferred technical scheme, the outlet of secondary hydrogenation reactor increases the entrance of pipeline connection one-level essence dealkylation reaction device, and the exchange achieving one-level essence dealkylation reaction device and secondary essence dealkylation reaction device uses.
The present invention is transformed by distribution pipes, and realizing secondary hydrogenation can be in parallel with one-level hydrogenation, use of also connecting.The beneficial effect of following three aspects can be produced after transformation: (1) solve hydrogen sulfide content lower than to enter on secondary hydrogenation hydrogen sulfide content in limited time secondary hydrogenation cannot bringing normally into operation as defect, played the benefit of existing equipment fully.(2) because one-level hydrogenation and secondary hydrogenation can in parallelly use, be equivalent to the disposal ability adding hydrogenation catalyst, as disposal ability does not increase, be equivalent to extend catalyst service life.(3) can be for subsequent use each other after one-level hydrogenation and secondary hydrogenation parallel connection, normally produce by another reactor maintenance of parallel connection when changing hydrogenation catalyst, do not need complete plant shutdown just can carry out.
Accompanying drawing explanation
Fig. 1 is the connection diagram of secondary catalyzing dehydrogen desulfurization in prior art.
Fig. 2 is the connection diagram of secondary catalyzing dehydrogen desulfurization of the present invention.
In figure, 1-pre-hydrogenator, 2-one-level hydrogenation reactor, 3-one-level essence dealkylation reaction device, 4-secondary hydrogenation reactor, 5-secondary essence dealkylation reaction device.
Detailed description of the invention
In order to make those skilled in the art better understand the present invention, below in conjunction with accompanying drawing, explanation clear, complete is further done to the present invention.
Secondary catalyzing dehydrogen desulfurization shown in Fig. 2, comprise pre-hydrogenator 1, one-level hydrogenation reactor 2, one-level essence dealkylation reaction device 3, secondary hydrogenation reactor 4 and the secondary essence dealkylation reaction device 5 of connecting successively, the outlet increase pipeline of described pre-hydrogenator 1 directly connects the entrance of secondary hydrogenation reactor 4.Utilize system shutdown to overhaul opportunity, pipeline is transformed, increases corresponding shearing device, realize one-level hydrogenation and secondary hydrogenation is used flexibly by valve transfer, can in parallelly use, use of also connecting.
Under normal circumstances, close the valve on the pipeline of increase, the flow process of unstripped gas is: pre-hydrogenator 1 → one-level hydrogenation reactor 2 → one-level essence dealkylation reaction device 3 → secondary hydrogenation reactor 4 → secondary essence dealkylation reaction device 5.
Reach when the hydrogen sulfide content after one-level hydrogenation reaction or prescribe a time limit lower than entering the upper of secondary hydrogenation reactor, open valve, the flow process of unstripped gas is: pre-hydrogenator 1 → one-level hydrogenation reactor 2 → one-level essence dealkylation reaction device 3.
Because one-level hydrogenation reactor and second reactor can exchange use, also can close one-level hydrogenation reactor entrance, the flow process of unstripped gas is changed into: pre-hydrogenator 1 → secondary hydrogenation reactor 4 → secondary essence dealkylation reaction device 5.
On the basis of above structure, increase the entrance of pipeline connection one-level essence dealkylation reaction device 3 in the outlet of secondary hydrogenation reactor 4.By closing or open corresponding entrance, the flow process of unstripped gas can have again two kinds of modes:
(1) pre-hydrogenator 1 → secondary hydrogenation reactor 4 → one-level essence dealkylation reaction device 3.
(2) pre-hydrogenator 1 → one-level hydrogenation reactor 2 → secondary essence dealkylation reaction device 5.
The scope of protection of present invention is not limited to above detailed description of the invention; to those skilled in the art; the present invention can have various deformation and change, all in design of the present invention and any amendment, the improvement done within principle be equal to replacement and all should be included within protection scope of the present invention.
Claims (2)
1. a secondary catalyzing dehydrogen desulfurization, comprise pre-hydrogenator (1), one-level hydrogenation reactor (2), one-level essence dealkylation reaction device (3), secondary hydrogenation reactor (4) and secondary essence dealkylation reaction device (5) of connecting successively, it is characterized in that: the outlet increase pipeline of described pre-hydrogenator (1) directly connects the entrance of secondary hydrogenation reactor (4).
2. secondary catalyzing dehydrogen desulfurization according to claim 1, is characterized in that: the outlet of secondary hydrogenation reactor (4) increases the entrance of pipeline connection one-level essence dealkylation reaction device (3).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510135149.5A CN104707453B (en) | 2015-03-26 | 2015-03-26 | Two-stage catalytic hydrodesulfurization device |
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|---|---|---|---|
| CN201510135149.5A CN104707453B (en) | 2015-03-26 | 2015-03-26 | Two-stage catalytic hydrodesulfurization device |
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| CN104707453B CN104707453B (en) | 2017-04-12 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105885997A (en) * | 2016-05-10 | 2016-08-24 | 湖北宜化集团有限责任公司 | Sodium removal device for high sodium coal |
| CN111439725A (en) * | 2020-03-21 | 2020-07-24 | 河南神马尼龙化工有限责任公司 | Hydrogen desulfurization system for device for producing cyclohexanol by partial hydrogenation of benzene and desulfurization method thereof |
| CN112725047A (en) * | 2020-12-03 | 2021-04-30 | 中昊黑元化工研究设计院有限公司 | Coal tar distillate hydrogenation modification and LNG preparation co-production process for comprehensive utilization of coke oven gas |
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2015
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20070277552A1 (en) * | 2006-02-10 | 2007-12-06 | Kaoru Fujimoto | Process for producing liquefied petroleum gas |
| CN101574622A (en) * | 2008-05-05 | 2009-11-11 | 韩松 | Dry-method desulphurization and deodorization technology with high efficiency low pressure drop |
| CN103396852A (en) * | 2013-07-17 | 2013-11-20 | 濮阳中石集团有限公司 | Double-tower natural gas desulfurization prying device and application method |
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| CN104031706A (en) * | 2014-05-27 | 2014-09-10 | 顾君尧 | Method for preparing natural gas by use of tail gas of calcium carbide furnace, and production device using same |
| CN204211707U (en) * | 2014-11-05 | 2015-03-18 | 新奥能源贸易有限公司 | Utilize the device of coke-oven gas and blast furnace gas combination producing Sweet natural gas and liquefied ammonia |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105885997A (en) * | 2016-05-10 | 2016-08-24 | 湖北宜化集团有限责任公司 | Sodium removal device for high sodium coal |
| CN111439725A (en) * | 2020-03-21 | 2020-07-24 | 河南神马尼龙化工有限责任公司 | Hydrogen desulfurization system for device for producing cyclohexanol by partial hydrogenation of benzene and desulfurization method thereof |
| CN112725047A (en) * | 2020-12-03 | 2021-04-30 | 中昊黑元化工研究设计院有限公司 | Coal tar distillate hydrogenation modification and LNG preparation co-production process for comprehensive utilization of coke oven gas |
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| Publication number | Publication date |
|---|---|
| CN104707453B (en) | 2017-04-12 |
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