CN1020333C - Method for alternating catalyst with carbon disulfide to sulfide cobalt-molybdenum - Google Patents

Method for alternating catalyst with carbon disulfide to sulfide cobalt-molybdenum Download PDF

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Publication number
CN1020333C
CN1020333C CN91102838A CN91102838A CN1020333C CN 1020333 C CN1020333 C CN 1020333C CN 91102838 A CN91102838 A CN 91102838A CN 91102838 A CN91102838 A CN 91102838A CN 1020333 C CN1020333 C CN 1020333C
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hours
temperature
catalyst
gram
sulfuration
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Expired - Fee Related
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CN91102838A
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CN1056090A (en
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陈劲松
李小定
华南平
王光厚
孔渝华
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HUBEI RESEARCH INSTITUTE OF CHEMISTRY
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HUBEI RESEARCH INSTITUTE OF CHEMISTRY
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The present invention relates to a method for vulcanizing Co-Mo sulfur resistant and carbon monoxide transformation catalyst by CS2, which aims to improve and perfect the method used in CN89100315.0. Catalysts are vulcanized by CS2 so that H2S can be penetrated at a temperature of 200 to 300DEGC, preferably a temperature of 230 to 270DEGC, namely that the concentration of H2S at the outlet is larger than 10 grams / standard meter<3>; the penetration is maintained for 1 to 6 hours, preferably 3 to 4 hours; at a temperature of 375 to 500 DEG C, high temperature vulcanization is preferably carried out at a temperature of 400 to 430 DEG C and is maintained for 1 to 6 hours, preferably 2 to 3 hours. Compared with the vulcanization method used in CN89100315.0, the method of the present invention enhances the catalyst activity about 10%.

Description

Method for alternating catalyst with carbon disulfide to sulfide cobalt-molybdenum
The present invention relates to the vulcanization process of cobalt molybdenum sulfur-resistant CO conversion catalyst, is the improvement to the described vulcanization process of CN89100315.0.
In the unstripped gas that the oil of present medium and small synthetic ammonia factory or coal are made, H 2S content is generally 1.5 gram/standard meters 3About, the nearly 5 gram/standard meters that have 3, if unstripped gas enters change furnace without desulfurization or partial desulfurization, then common Cu-Zu is that low temperature conversion catalyst will be inapplicable because of being subjected to sulfur poisoning, Fe-Cr be high temperature conversion catalyst because of not anti-high sulfur content, the active temperature height, transformationreation is incomplete, the consumption quantity of steam is big, so also inapplicable.For each state of energy-saving and production-increase has all developed the good Co-Mo of the low temperature active of anti-sulphur is transformation catalyst.
U, S, Pat No 3,850,840, U, S, Pat No 3,957,962, U, S, Pat No 4,153,580 and U, S Pat No 4,166,101 grades have been reported with Ai 2O 3For the Co-Mo of carrier is a sulfur-resistant transformation catalyst, and lower active temperature is arranged, (CN87107892) sulfur-resistant transformation catalyst of developments such as Hubei Prov. Chemical Research Inst has more excellent low temperature active.
Co-Mo is that sulfur-resistant CO conversion catalyst all needs can use through over cure usually.Vulcanization process condition has material impact to activity, and the opinion that has＜320 ℃ warm ya is sulfuration down, sees the C of U.S. UCI company 25-2-02The specification of catalyst, BASF sulfur-resistant transformation catalyst K 8-11Operation instructions, CN89100315.0 advocate to be preferably under 350-400 ℃ and to use H 250-450 ℃ of sulfuration down 2S or CS 2Sulfuration, vulcanizing agent concentration 1-4%, experiment cure time 3.5-4.5 hour.But H during all unlisted sulfuration 2The temperature and time that S penetrates feeds change furnace though CN90102615 has proposed directly to make high-sulfur coal gas with solid sulfurizing agent or sulphur coal, makes its H under change furnace＜200 ℃ 2S penetrates, but the unlisted data that penetrate with activity relationship.
The present invention is that its objective is provides a kind of optimum cure technology to CN89100315,0 improvement and improvement, and making Co-Mo is that sulfur-resistant CO conversion catalyst has excellent low temperature active after sulfuration.
The objective of the invention is to adopt following technique measures to realize, is sulfur-resistant CO conversion catalyst CS with Co-Mo 2Heat up and vulcanize, curing temperature is since 200 ℃, at 200-300 ℃ of following H 2S penetrates, and better penetrates outlet H at 230-270 ℃ 2S concentration is at 10 gram/standard meters 3More than, and under this concentration, kept 1-6 hour, for saving time province more preferably 3-4 hour, continue sulfuration then, and be warming up to 375-500 ℃ gradually and vulcanized 1-6 hour, better under 400-430 ℃, vulcanized 2-3 hour, import and export H this moment 2S concentration should be greater than 10 gram/standard meters 3
The catalyst activity property testing is that the tube inner diameter that carries out in not smashing former testing graininess device to pieces is 32 millimeters, and catalyst volume is 30 milliliters, air speed 1000 hours -1, automobile is than 1.0, normal pressure, and semiwater gas, 190 ℃ of temperature are actively represented with the carbon monodixe conversion rate.
Accompanying drawing 1-5 represents to penetrate temperature, time of break-through, and strong curing temperature, strong cure time are to the influence of activity.
Fig. 1, H 2S penetrates the influence of temperature to catalyst activity, and condition is to penetrate back constant temperature 2 hours, strengthens sulfuration 3 hours down for 375 ℃ then.
Fig. 2, H 2S penetrates the influence of back constant temperature time to catalyst activity, and condition is at 250 ℃ of following H 2S penetrates, and vulcanizes 3 hours down at 375 ℃ then.
Fig. 3,4, H 2The strong curing temperature of S is to the influence of catalyst activity, and condition is at 250 ℃ of following H 2S penetrated 3 hours, strong respectively then sulfuration 2.5 hours and 2 hours.
Fig. 5, H 2The strong cure time of S is to the influence of catalyst activity, and condition is 250 ℃ of following H 2S penetrated 3 hours, then 410 ℃ strong down sulfurations.
Embodiment 1
Get the catalyst sample of production, use CS 2Vulcanize, be warmed up to 200 ℃ naturally from room temperature and begin to add CS 2, vulcanizing agent concentration is with H 2S counts 15 gram/standard meters 3, continue to be warmed up to 375 ℃ of sulfurations 3 hours, recording shift activity is 85.6%.
Embodiment 2
Sample is used CS with example 1 2Vulcanize, be warmed up to 200 ℃ naturally from room temperature and begin to add CS 2, concentration is with H 2S counts 15 gram/standard meters 3, be warming up to 300 ℃, treat H 2S penetrates, and promptly exports H 2S＞10 gram/standard meters 3After, constant temperature 2 hours, and then be warming up to 375 ℃ of maintenances 3 hours, recording shift activity is 89.7%.
Embodiment 3
Sample is used CS with example 1 2Sulfuration is warmed up to 200 ℃ naturally from room temperature and begins to add CS 2, concentration is with H 2S counts 15 gram/standard meters 3,, treat H at 200 ℃ of constant temperature 2S penetrates and promptly exports H 2S＞10 gram/standard meters 3After, keep 2 hours again, and then be warming up to 375 ℃ of insulations 3 hours, record shift activity 88.6%.
Embodiment 4
Sample is used CS with example 1 2Sulfuration is warmed up to 200 ℃ naturally from room temperature and begins to add CS 2, concentration is with H 2S counts 15 gram/standard meters 3,, treat H at 250 ℃ of constant temperature 2S penetrates and promptly exports H 2S＞10 gram/standard meters 3After, kept again 3 hours, be warming up to 375 ℃, kept 3 hours, record shift activity 91.1%.
Embodiment 5
Sample is used CS with example 1 2Sulfuration is warmed up to 200 ℃ naturally from room temperature and begins to add CS 2, concentration is with H 2S counts 15 gram/standard meters 3,, treat H at 250 ℃ of constant temperature 2S penetrates and promptly exports H 2S＞10 gram/standard meters 3After, kept again 1 hour, be warming up to 375 ℃ and kept 3 hours, record shift activity 90.2%.
Embodiment 6
Remove H 2S penetrates outside the constant temperature 6 hours, and other is operated with embodiment 5, records shift activity 92.7%.
Embodiment 7
Sample is used CS with example 1 2Sulfuration is warmed up to 200 ℃ naturally from room temperature and begins to add CS 2, concentration is with H 2S counts 15 gram/standard meters 3,, get H at 250 ℃ of constant temperature 2S penetrates and promptly exports H 2S＞10 gram/standard meters 3After, kept again 6 hours, be warming up to 375 ℃ and kept 1 hour, record shift activity 90.3%.
Embodiment 8
Sample is used CS with example 1 2Sulfuration is warmed up to 200 ℃ naturally from room temperature and begins to add CS 2, concentration is with H 2S counts 15 gram/standard meters 3,, get H at 250 ℃ of constant temperature 2S penetrates and promptly exports H 2S＞10 gram/standard meters 3After, kept again 3 hours, be warming up to 410 ℃, kept 1 hour, record shift activity 93.0%.
Embodiment 9
Condition keeps 2.5 hours except that being warming up to 410 ℃, and other condition records shift activity 95.7% with embodiment 8.
Embodiment 10
Sample is used CS with example 1 2Sulfuration is warmed up to 200 ℃ naturally from room temperature and begins to add CS 2, concentration is with H 2S counts 15 gram/standard meters 3, treat H at 250 ℃ of constant temperature 2S penetrates and promptly exports H 2S＞10 gram/standard meters 3After, kept again 3 hours, be warming up to 450 ℃, kept 2.5 hours, record shift activity 95.0%.
Embodiment 11
Sample is used CS with example 1 2Sulfuration is warmed up to 200 ℃ naturally from room temperature, begins to add CS 2, concentration is with H 2S counts 15 gram/standard meters 3,, treat H at 250 ℃ of constant temperature 2S penetrates, outlet H 2S＞10 gram/standard meters 3After, kept again 3 hours, be warming up to 500 ℃ and kept 2 hours, record shift activity 94.0%.
Embodiment 12
Sample is used CS with example 1 2Sulfuration is warmed up to 200 ℃ naturally from room temperature and begins to add CS 2, concentration is with H 2S counts 15 gram/standard meters 3,, treat H at 250 ℃ of constant temperature 2S penetrates, outlet H 2S＞10 gram/standard meters 3After, kept again 3 hours, be warming up to 450 ℃ and kept 2 hours, recording shift activity is 94.5%.
Embodiment 13
The Co-Mo that gets the preparation of different process method is a sulfur-resistant CO conversion catalyst, adopts above-mentioned test condition, and influence sees Table 1 to its sulfuration process to catalyst activity.
Embodiment 14
Get 6 meters 3Co-Mo is in the low change stove of sulfur-resistant CO conversion catalyst (Hubei Prov. Chemical Research Inst produce EB-4 catalyst) the identical production system of two covers that is loaded on certain synthesis ammonia plant (Beijing), adopt CN89100315,0 method and the inventive method to vulcanize respectively, the result is as shown in table 2.
First and second liang of other conversion working conditions of system such as steam-to-gas ratio, air speed, pressure, unstripped gas composition etc. are identical.
More excellent than other vulcanization process from above-mentioned table 1, table 2 data vulcanization process of the present invention as can be seen, the Co-Mo transformation catalyst that vulcanized has better low temperature active.
Table 1 vulcanization process condition is to the influence of catalyst activity (interconversion rate %)
The sulfuration process traditional C 2Sulfuration CN89100315,0 the inventive method *
Interconversion rate % T＜320 ℃ of method *
Catalyst
Homemade A(Hubei) 88.0 92.2 95.7
Homemade B(Hubei) 75.1 80.7 85.6
External C(Denmark) 72.6 77.7 81.7
The results of industrial application of table 2 catalyst vulcanization technology relatively
Transformation system vulcanization process inlet temperature import CO exports CO
First CN89100315,0 180 ℃ of 5-6% 1-1.5%
165 ℃ of 5-6% 1-1.5% of second * of the present invention

Claims (5)

1, Co-Mo is that sulfur-resistant CO conversion catalyst utilizes CS 2The method of vulcanizing, catalyst temperature rise to 200 ℃ begin to add CS 2, concentration is with H 2S counts about 15 gram/standard meters 3, it is characterized in that at 200-300 ℃ of following H 2S penetrated 1-6 hour, continued sulfuration then and be warming up to gradually to vulcanize H under 375-500 ℃ 1-6 hour 2The S breakthrough concentration is greater than 10 gram/standard meters 3
2, vulcanization process as claimed in claim 1 is characterized in that better at 230-270 ℃ of following H 2S penetrates.
3, vulcanization process as claimed in claim 1 or 2 is characterized in that H 2S time of break-through more preferably 3-4 hour.
4, vulcanization process as claimed in claim 1 is characterized in that more preferably 400-430 ℃ of high temperature vulcanized temperature.
5,, it is characterized in that more preferably 2-3 hour high temperature vulcanized time as the vulcanization process of claim 1 or 4.
CN91102838A 1991-04-27 1991-04-27 Method for alternating catalyst with carbon disulfide to sulfide cobalt-molybdenum Expired - Fee Related CN1020333C (en)

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CN1020333C true CN1020333C (en) 1993-04-21

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6365542B1 (en) * 1999-01-25 2002-04-02 China Petrochemical Corporation And Research Institute Of Petroleum Processing Presulfurization method of hydrogenation catalyst
CN103059910B (en) * 2011-10-21 2014-12-31 中国石油化工股份有限公司 Vulcanization method of hydrofining catalyst

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

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