CN104707453B

CN104707453B - Two-stage catalytic hydrodesulfurization device

Info

Publication number: CN104707453B
Application number: CN201510135149.5A
Authority: CN
Inventors: 卢燊; 庄兰军; 李坤杰; 原佳强
Original assignee: Shanxi Provincial Guoxin Energy Development Group Co Ltd
Current assignee: Shanxi Provincial Guoxin Energy Development Group Co Ltd
Priority date: 2015-03-26
Filing date: 2015-03-26
Publication date: 2017-04-12
Anticipated expiration: 2035-03-26
Also published as: CN104707453A

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

Two grades of catalyzing dehydrogen desulfurizations

Technical field

The present invention relates to coal（Coke-stove gas）Two grades of catalytic desulfurhydrogenations dress of the chemicals raw material such as preparing natural gas, methanol Put.

Background technology

At present, in New Coal Chemical field, coal（Coke-stove gas）The chemicals such as preparing natural gas, methanol unstripped gas is slightly taking off Fine desulfurizing technology flow process after sulfur is generally：Pre- hydrogenation, one-level hydrogenation, a fine de-sulfur, secondary hydrogenation, two fine de-sulfurs（Fig. 1）.Just Above-mentioned process operation is pressed in the case of often, removing requirement of the subsequent process to total sulfur content is can reach（Below 0.1PPM）.Wherein one Level hydrogenation and secondary hydrogenation device effect be by the organic sulfurs such as raw material cos therein, mercaptan, thiophene catalyst work With lower generation hydrogenation reaction, inorganic hydrogen sulfide is generated, to be removed in two-stage fine de-sulfur device.Catalytic hydrogenation reaction device The hydrogenation reaction of middle generation is as follows：

COS (cos)+H₂→ CO+H₂S

RSH（Mercaptan）+ H₂→ RH+H₂S

C₄H₄S (thiophene)+4H₂→C₄H₁₀+ H₂S

The chemical reaction occurred in two-stage fine de-sulfur reactor is as follows：

Z_N0+H₂S→Z_NS+H₂O

But if because coking is with coal sulfur content is low, the original such as upstream wet desulfurization system desulfurized effect is good in actual production Cause, the unstripped gas hydrogen sulfide index into cleaning system is far below design load so that the hydrogen sulfide content after one stage catalyzing hydrogenation At or below the lower limit into two grades of catalytic hydrogenation reaction devices.Now as gas enters back into secondary hydrogenation, will be in secondary hydrogenation There is inverse sulphureting reaction under anaerobic environment in reactor, the hydrogen sulfide content into subsequent process is increased on the contrary.Devulcanization Acting chemical reaction is as follows：

2CH₃CHOHCOOH H₂SO₄→2CH₃COOH 2CO₂ H₂S

In this case, secondary hydrogenation device just cannot normally come into operation, and not play due effect.Meanwhile, according to original Technological process, one-level hydrogenation and secondary hydrogenation because being used in series, during replacing one-level hydrogenation catalyst must complete plant shutdown just can enter OK.

The content of the invention

The technical problem to be solved in the present invention is to provide a kind of two grades of catalyzing dehydrogen desulfurizations, and the device can avoid two grades There is inverse sulphureting reaction in hydrogenation reactor.

To solve above technical problem, the present invention is improved on the basis of existing two grades of catalyzing dehydrogen desulfurizations.

A kind of two grades of catalyzing dehydrogen desulfurizations of the present invention, including the pre-hydrogenator, one-level that are sequentially connected in series Hydrogenation reactor, one-level loss of essence reactor, secondary hydrogenation reactor and two grades of loss of essence reactors, described pre-hydrogenator Outlet increases the entrance that pipeline is directly connected to secondary hydrogenation reactor.Flow process is after transformation：Pre- hydrogenation, one-level hydrogenation and two grades add Hydrogen in parallel or series, a fine de-sulfur, two fine de-sulfurs.Hydrogen sulfide content after one-level hydrogenation reaction is at or below into two grades During the upper limit of hydrogenation reactor, the entrance of secondary hydrogenation reactor is closed, unstripped gas is only anti-through one-level hydrogenation after pre- hydrogenation Device and one-level loss of essence reactor are answered, so avoids that inverse sulphureting reaction occurs in secondary hydrogenation reactor.

Used as preferred technical scheme, the outlet of secondary hydrogenation reactor increases entering for pipeline connection one-level loss of essence reactor Mouthful, realize the used interchangeably of one-level loss of essence reactor and two grades of loss of essence reactors.

The present invention is transformed by distribution pipes, realizes that secondary hydrogenation can be in parallel with one-level hydrogenation, also can be used in series.Transformation The beneficial effect of following three aspect can be produced afterwards：（1）Solve in hydrogen sulfide content less than into secondary hydrogenation hydrogen sulfide content During the upper limit secondary hydrogenation cannot bringing normally into operation such as defect, fully played the benefit equipped.（2）Due to one-level hydrogenation and Secondary hydrogenation can be used in parallel, and equivalent to the disposal ability that increased hydrogenation catalyst, such as disposal ability does not increase, equivalent to prolongation Catalyst service life.（3）Can be standby each other after one-level is hydrogenated with and secondary hydrogenation is in parallel, can pass through when changing hydrogenation catalyst Another reactor in parallel maintains normal production, and being not required to complete plant shutdown can be carried out.

Description of the drawings

Fig. 1 is the connection diagram of two grades of catalyzing dehydrogen desulfurizations in prior art.

Fig. 2 is the connection diagram of two grades of catalyzing dehydrogen desulfurizations of the invention.

In figure, 1- pre-hydrogenators, 2- one-level hydrogenation reactors, 3- one-level loss of essence reactors, the reaction of 4- secondary hydrogenations Device, bis- grades of loss of essence reactors of 5-.

Specific embodiment

In order that those skilled in the art are better understood from the present invention, make further clear to the present invention below in conjunction with accompanying drawing Chu, complete explanation.

Two grades of catalyzing dehydrogen desulfurizations shown in Fig. 2, it is anti-including pre-hydrogenator 1, the one-level hydrogenation being sequentially connected in series Answer device 2, one-level loss of essence reactor 3, secondary hydrogenation reactor 4 and two grades of loss of essence reactors 5, described pre-hydrogenator 1 Outlet increases the entrance that pipeline is directly connected to secondary hydrogenation reactor 4.Opportunity is overhauled using system shutdown, pipeline is changed Make, increase corresponding shearing device, realize that one-level hydrogenation and secondary hydrogenation are flexibly used by valve transfer, can be used in parallel, Also can be used in series.

Under normal circumstances, the valve closed on increased pipeline, the flow process of unstripped gas is：Pre-hydrogenator 1 → mono- Level hydrogenation reactor 2 → one-level loss of essence 3 → secondary hydrogenation of reactor 4 → bis- grades of loss of essence reactors 5 of reactor.

When the hydrogen sulfide content after one-level hydrogenation reaction is at or below the upper limit into secondary hydrogenation reactor, open Valve, the flow process of unstripped gas is：Pre-hydrogenator 1 → one-level hydrogenation reactor 2 → one-level loss of essence reactor 3.

Because one-level hydrogenation reactor and second reactor can be with used interchangeablies, it is also possible to close one-level hydrogenation reactor and enter Mouthful, the flow process for making unstripped gas is changed into：1 → secondary hydrogenation of pre-hydrogenator reactor, 4 → bis- grades of loss of essence reactors 5.

On the basis of above structure, in the outlet of secondary hydrogenation reactor 4 pipeline connection one-level loss of essence reactor 3 is increased Entrance.By turning off or on corresponding entrance, the flow process of unstripped gas can have two ways again：

（1）Pre-hydrogenator 1 → secondary hydrogenation reactor 4 → one-level loss of essence reactor 3.

（2）1 → one-level of pre-hydrogenator hydrogenation reactor, 2 → bis- grades of loss of essence reactors 5.

The scope of protection of present invention is not limited to above specific embodiment, to those skilled in the art, this Invention can have various deformation and a change, all designs in the present invention and any modification, improvement made within principle and be equal to Replacement all should be included within protection scope of the present invention.

Claims

1. a kind of two grades of catalyzing dehydrogen desulfurizations, including the pre-hydrogenator being sequentially connected in series（1）, one-level hydrogenation reactor （2）, one-level fine de-sulfur reactor（3）, secondary hydrogenation reactor（4）With two grades of fine de-sulfur reactors（5）, it is characterised in that：Institute The pre-hydrogenator stated（1）Outlet increase pipeline be directly connected to secondary hydrogenation reactor（4）Entrance；When one-level is hydrogenated with instead Should after hydrogen sulfide content at or below the upper limit into secondary hydrogenation reactor when, close entering for secondary hydrogenation reactor Mouthful, unstripped gas is after pre- hydrogenation only through one-level hydrogenation reactor and one-level fine de-sulfur reactor；

Secondary hydrogenation reactor（4）Outlet increase pipeline connection one-level fine de-sulfur reactor（3）Entrance；One-level fine de-sulfur is anti- Answer device and two grades of fine de-sulfur reactor used interchangeablies.