CN101733171A - Emptying-free complete circulation vulcanizing method for Co-Mo sulfur tolerant shift catalyst vulcanizing process gas - Google Patents
Emptying-free complete circulation vulcanizing method for Co-Mo sulfur tolerant shift catalyst vulcanizing process gas Download PDFInfo
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- CN101733171A CN101733171A CN200910273129A CN200910273129A CN101733171A CN 101733171 A CN101733171 A CN 101733171A CN 200910273129 A CN200910273129 A CN 200910273129A CN 200910273129 A CN200910273129 A CN 200910273129A CN 101733171 A CN101733171 A CN 101733171A
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- Prior art keywords
- emptying
- gas
- sulfuration
- vulcanizing
- sulfur
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- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000011593 sulfur Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000004073 vulcanization Methods 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 230000000977 initiatory effect Effects 0.000 claims abstract description 4
- 238000005987 sulfurization reaction Methods 0.000 claims description 30
- 230000009466 transformation Effects 0.000 claims description 18
- 230000001186 cumulative effect Effects 0.000 claims description 5
- 239000002699 waste material Substances 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000005486 sulfidation Methods 0.000 description 4
- 239000008234 soft water Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
The invention relates to an emptying-free complete circulation vulcanizing method for a Co-Mo sulfur tolerant shift catalyst vulcanizing process gas. In the method, by utilizing the initial activity of Co-Mo sulfur tolerant shift catalyst after being partially vulcanized, a vulcanized circulatory gas is properly moistened so that CO and H2O react to generate CO2 and H2, H2 needed by vulcanization reaction is generated, and the moistening degree is the temperature of the gas charged into a Roots blower, which is controlled in a range of 25-55 DEG C, preferably in a range of 30-40 DEG C; an emptying-free circulatory vulcanized air flow is slightly larger than an emptied or partially emptied vulcanizing air flow, and the quantity is between 200-300h<-1> metered by the total volume of catalyst, preferably 220-260h<-1>. The circulation vulcanizing method solves the problems of pollution and waste caused by emptying vulcanization and greatly reduces the activating cost.
Description
Technical field
The present invention relates to the vulcanization process that not emptying of sulfiding gas recycles in the Co-Mo catalyst vulcanization process, specifically, relate to gases such as sulfur-bearing, the hydrogen method that its not emptying of gas recycles in handling Co-Mo sulfur-resistant transformation catalyst sulfidation.
Background technology
At the conversion section of Ammonia Production, need to use a kind of Co-Mo sulfur-resistant transformation catalyst, this catalyst will be used sulfur-bearing (H before use
2S) and hydrogen carry out activation processing, be commonly called as " sulfuration ", make catalyst be converted into sulphided state by oxidation state, could satisfy instructions for use, sulfuration needs certain temperature, tolerance and time, sulfuration is made of following reaction:
CS
2+4H
2→2H
2S+CH
4；CoO+H
2S→CoS+H
2O
MoO
3+H
2+2H
2S→MoS
2+3H
2O
The H of reaction needed
2Mainly the semiwater gas that send from gas making workshop section (mainly form: N by semiwater gas
2:～40%, CO
2:～8%, CO :～30%), H
2S is mainly from the vulcanizing agent CS that adds
2Constantly consume H in the whole sulfidation
2, H
2S.In order to guarantee cure efficiency, require the H in the gas
2S 〉=5g/Nm
3, H
2〉=25%, so sulfiding gas sends into the change furnace that catalyst is housed continuously, contains the intact H of unreacted
2, H
2Emptying or the part emptying behind change furnace continuously of gases such as S, part circulation; Its result causes the waste of environmental pollution, semiwater gas and vulcanizing agent to consume problems such as height.
Summary of the invention
The vulcanization process that the purpose of this invention is to provide a kind of not emptying of Co-Mo sulfur-resistant transformation catalyst sulfidation gas complete alternation.This method compared with prior art can guarantee the validity of recyclegas to the sulfuration of Co-Mo sulfur-resistant transformation catalyst, can allow again and vulcanize not emptying of gas, thereby solve the drawback that prior art exists, and reduces the sulfuration cost significantly, has eliminated pollution substantially.
Purpose of the present invention adopts following proposal to realize: Co-Mo sulfur-resistant transformation catalyst sulfurizing treatment method, it is characterized in that the sulfiding gas complete alternation utilizes the method for not emptying, utilize the initial activity after the partial vulcanization of Co-Mo sulfur-resistant transformation catalyst, suitably humidification sulfuration back recyclegas makes it to take place CO+H
2O → CO
2+ H
2Transformationreation produces the required H of vulcanization reaction
2, the degree of humidification is that control is gone into the temperature of roots blower gas in 25～55 ℃ of scopes; The circulating sulfuration tolerance of not emptying is more bigger than the tolerance of emptying or part emptying sulfuration, its quantity in the catalyst cumulative volume at 200～300h
-1Between.
Preferred version of the present invention is:
The degree of described sulfuration back recyclegas humidification is that control is gone into the temperature of roots blower gas in 30～40 ℃ of scopes.
The circulating sulfuration tolerance of described not emptying is more bigger than the tolerance of emptying or part emptying sulfuration, its quantity in the catalyst cumulative volume at 220～260h
-1Between.
Description of drawings
Fig. 1. prior art is to the artwork of Co-Mo sulfur-resistant transformation catalyst vulcanizing treatment
Fig. 2. the present invention is to the artwork of Co-Mo sulfur-resistant transformation catalyst vulcanizing treatment
Number in the figure implication: 1. roots blower, 2. saturated hot-water tower, 3. water recirculator, 4. electric furnace, 5. change furnace, the 6. first water heat exchanger, 7. hot water circulating pump, 8. soft water heat exchanger, 9. moisture separator.
The specific embodiment:
With reference to accompanying drawing in detail, specific implementation method of the present invention is described in detail.
In Fig. 1, traditional way is: the semiwater gas that carry in the gas making post is delivered to electric furnace 4 through the roots blower 1 of conversion section, and the back of heating up adds vulcanizing agent CS
2, enter the change furnace 5 that the Co-Mo sulfur-resistant transformation catalyst is housed again, carry out vulcanization reaction by the sulfuration scheme.Sulfuration gas emptying behind change furnace of the heat after the sulfuration enters atmosphere; When adopting part to circulate emptying, go out the sulfuration gas of the heat of change furnace, the emptying behind change furnace of 30～50% portion gas, another part sulfuration gas enters the first water heat exchanger 6 (this water heater is as crossing the gas passage not to the gas cooling), (hot water circulating pump is inoperative to reenter saturated hot-water tower 2, saturated hot-water tower does not have recirculated water) reenter then soft water heat exchanger 8 indirectly the cooling cooling after moisture separator 9 minutes is dried up, gas enters roots blower to be mixed with fresh semiwater gas that the gas making post is sent here and reenters the conversion curing system, carries out vulcanization reaction continuously.
Fig. 2 has provided the approach that described sulfiding gas complete alternation of the present invention is used: the semiwater gas that carry in the gas making post is delivered to electric furnace 4 through the roots blower 1 of conversion section, and the back of heating up adds vulcanizing agent CS
2Enter the change furnace 5 that the Co-Mo sulfur-resistant transformation catalyst is housed again, carry out vulcanization reaction by the sulfuration scheme, go out the not emptying of sulfuration gas (starting hot water circulating pump before advancing the first water heat exchanger 6) of the sulfuration after heat of change furnace, going into the first water heat exchanger 6 lowers the temperature indirectly, reenter saturated hot-water tower 2, reenter soft water heat exchanger 8 with the reverse humidification that contacts of the recirculated water of saturated hot-water tower, further cooling cooling, after moisture separator 9 minutes is dried up, reenter roots blower again and deliver to change furnace, recycle whole not exhaust of not emptying of process.
In the process of not emptying of sulfiding gas complete alternation, H
2S, H
2Participate in the vulcanization reaction of Co-Mo sulfur-resistant transformation catalyst, the H that unreacted is intact
2S, H
2Use repeatedly with circulating air; H
2S, H
2Concentration will dwindle gradually, in order to guarantee H in the gas
2The valid density of S, CS
2Constantly add hydrogenolysis generation H takes place
2S; H
2The source mainly from H contained in the semiwater gas
2, because not emptying, air compensation is limited, only can replenish the volume of the portion gas that consumes owing to vulcanization reaction, along with the carrying out of vulcanization reaction, and H
2Valid density can descend H
2Valid density do not reach requirement, the invention provides the initial activity that is had after the partial vulcanization of a kind of Co-Mo of utilization sulfur-resistant transformation catalyst, make it to take place CO+H
2O → CO
2+ H
2Transformationreation, thereby section H is provided
2When sulfuration after after a while, 50% of total approximately cure time～70% o'clock, the H in the coal gas
2Concentration be difficult to satisfy the requirement of vulcanization reaction, control this moment is advanced the temperature of the sulfiding gas behind the roots blower inlet humidification between 25～55 ℃, be preferably between 30～40 ℃, the saturation vapour behind the contained humidification of circulating sulfuration gas can reach above-mentioned transformationreation and mend H
2Purpose, thereby can finish follow-up vulcanization reaction.Wherein, suitable circulating flow rate is essential.The internal circulating load of not emptying is more bigger than the tolerance of emptying or part emptying sulfuration, its quantity in the catalyst cumulative volume at 200～300h
-1Better, preferably at 220～260h
-1Between.Because be subjected to the restriction of change furnace power and relevant device, excessive internal circulating load is worthless.
The vulcanization process of gas complete alternation not emptying sulfuration of the present invention and emptying or part emptying compares: the former can reach the same cure efficiency with the latter, and can reduce even eliminate pollution significantly to atmosphere, add vulcanizing agent and can reduce by 30%～50%, the semiwater gas requirement significantly reduces, and the sulfuration cost declines to a great extent.Whole not emptying of gas total recycle process does not need other increase equipment, simple possible.
Embodiment: the vulcanization process of not emptying of Co-Mo catalyst vulcanization process gas complete alternation of the present invention, tentative at a plurality of synthesis ammonia plants such as Henan, northeast, respond well.
Following table is to having vulcanization process and vulcanization process of the present invention in handling Co-Mo sulfur-resistant transformation catalyst process, the consumption situation of vulcanizing agent and semiwater gas, and behind this catalyst vulcanization under identical working condition, complete low become its activity of such catalysts situation in the production process.
Claims (3)
1. a Co-Mo sulfur-resistant transformation catalyst sulfurizing treatment method is characterized in that the sulfiding gas complete alternation utilizes the method for not emptying, utilizes the initial activity after the partial vulcanization of Co-Mo sulfur-resistant transformation catalyst, and suitably humidification sulfuration back recyclegas makes it to take place CO+H
2O → CO
2+ H
2Transformationreation produces the required H of vulcanization reaction
2, the degree of humidification is that control is gone into the temperature of roots blower gas in 25～55 ℃ of scopes; The circulating sulfuration tolerance of not emptying is more bigger than the tolerance of emptying or part emptying sulfuration, its quantity in the catalyst cumulative volume at 200～300h
-1Between.
2. Co-Mo sulfur-resistant transformation catalyst sulfurizing treatment method as claimed in claim 1 is characterized in that, the degree of described sulfuration back recyclegas humidification is that control is gone into the temperature of roots blower gas in 30～40 ℃ of scopes.
3. Co-Mo sulfur-resistant transformation catalyst sulfurizing treatment method as claimed in claim 1 is characterized in that, the circulating sulfuration tolerance of described not emptying is more bigger than the tolerance of emptying or part emptying sulfuration, its quantity in the catalyst cumulative volume at 220～260h
-1Between.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102731299A CN101733171B (en) | 2009-12-08 | 2009-12-08 | Emptying-free complete circulation vulcanizing method for Co-Mo sulfur tolerant shift catalyst vulcanizing process gas |
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|---|---|---|---|
| CN2009102731299A CN101733171B (en) | 2009-12-08 | 2009-12-08 | Emptying-free complete circulation vulcanizing method for Co-Mo sulfur tolerant shift catalyst vulcanizing process gas |
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| Publication Number | Publication Date |
|---|---|
| CN101733171A true CN101733171A (en) | 2010-06-16 |
| CN101733171B CN101733171B (en) | 2012-05-23 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102500427A (en) * | 2011-10-21 | 2012-06-20 | 山西省霍州市化学工业有限责任公司 | Curing method of novel catalyst |
| CN102584533A (en) * | 2012-01-18 | 2012-07-18 | 新疆天业（集团）有限公司 | Superlow-sulfur and high-concentration CO gas exchange sulfur supplementation and cyclic utilization method |
| CN102784669A (en) * | 2012-08-17 | 2012-11-21 | 中国石油化工集团公司 | Individual activating process for catalysts in converting furnaces of CO (carbon oxide) sulfur-resistant converting device |
| CN103657740A (en) * | 2012-09-19 | 2014-03-26 | 中国石油化工股份有限公司 | Step-by-step sulfuration method of sulfur tolerant shift catalyst |
| CN103657741A (en) * | 2012-09-19 | 2014-03-26 | 中国石油化工股份有限公司 | Method for circularly and rapidly pre-vulcanizing sulfur tolerant shift catalyst and carrying out segmental pre-vulcanizing by utilizing sulfur tolerant shift catalyst |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061633C (en) * | 1997-07-23 | 2001-02-07 | 湖北省化学研究所 | Multi-function iron oxide fine sweetening agent and preparation thereof |
| CN1063102C (en) * | 1997-09-25 | 2001-03-14 | 湖北省化学研究所 | Method for activation recovering of cobalt-molybdenum sulfur-resisting transformation catalyst |
-
2009
- 2009-12-08 CN CN2009102731299A patent/CN101733171B/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102500427A (en) * | 2011-10-21 | 2012-06-20 | 山西省霍州市化学工业有限责任公司 | Curing method of novel catalyst |
| CN102584533A (en) * | 2012-01-18 | 2012-07-18 | 新疆天业（集团）有限公司 | Superlow-sulfur and high-concentration CO gas exchange sulfur supplementation and cyclic utilization method |
| CN102784669A (en) * | 2012-08-17 | 2012-11-21 | 中国石油化工集团公司 | Individual activating process for catalysts in converting furnaces of CO (carbon oxide) sulfur-resistant converting device |
| CN103657740A (en) * | 2012-09-19 | 2014-03-26 | 中国石油化工股份有限公司 | Step-by-step sulfuration method of sulfur tolerant shift catalyst |
| CN103657741A (en) * | 2012-09-19 | 2014-03-26 | 中国石油化工股份有限公司 | Method for circularly and rapidly pre-vulcanizing sulfur tolerant shift catalyst and carrying out segmental pre-vulcanizing by utilizing sulfur tolerant shift catalyst |
| CN103657740B (en) * | 2012-09-19 | 2015-05-20 | 中国石油化工股份有限公司 | Step-by-step sulfuration method of sulfur tolerant shift catalyst |
| CN103657741B (en) * | 2012-09-19 | 2015-10-14 | 中国石油化工股份有限公司 | A kind of sulfur-resistant transformation catalyst circulates quick presulfurization and utilize it to carry out segmentation method for pre-sulphuration |
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| Publication number | Publication date |
|---|---|
| CN101733171B (en) | 2012-05-23 |
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| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: The sulfurization method of Co Mo sulfur tolerant shift catalyst without gas venting and full circulation during the sulfurization process Granted publication date: 20120523 Pledgee: Yunongshang Financial Leasing Co.,Ltd. Pledgor: HAISO TECHNOLOGY Co.,Ltd. Registration number: Y2024980030801 |
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