CN1018796B - Solid vulcanizing agnet for cobalt-molybdenum series catalyst vulcanization and preparation thereof - Google Patents

Solid vulcanizing agnet for cobalt-molybdenum series catalyst vulcanization and preparation thereof

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Publication number
CN1018796B
CN1018796B CN90104955A CN90104955A CN1018796B CN 1018796 B CN1018796 B CN 1018796B CN 90104955 A CN90104955 A CN 90104955A CN 90104955 A CN90104955 A CN 90104955A CN 1018796 B CN1018796 B CN 1018796B
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CN
China
Prior art keywords
sulfur
additive
sulfurizing agent
vulcanizing agent
solid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CN90104955A
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Chinese (zh)
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CN1048175A (en
Inventor
薛全康
郭慎远
吴大天
马步勇
陈劲松
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
HUBEI RESEARCH INSTITUTE OF CHEMISTRY
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HUBEI RESEARCH INSTITUTE OF CHEMISTRY
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Application filed by HUBEI RESEARCH INSTITUTE OF CHEMISTRY filed Critical HUBEI RESEARCH INSTITUTE OF CHEMISTRY
Priority to CN90104955A priority Critical patent/CN1018796B/en
Publication of CN1048175A publication Critical patent/CN1048175A/en
Publication of CN1018796B publication Critical patent/CN1018796B/en
Expired legal-status Critical Current

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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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • 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

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Abstract

The present invention relates to a solid sulfurizing agent used for the sulfurization of Co-Mo carbon monoxide conversion catalysts and a preparation method thereof. The sulfurizing agent is prepared from elemental sulfur or the sulfur containing compounds such as ammonium polysulfide, sodium polysulfide, iron sulfide, etc., additives (inorganic oxide or sulfide containing double key high polymers, sulfurizing agents or transition elements), carriers such as Al2O3, SiO2, ZnO and MgO, diatomite and adhesives such as water glass or gypsum or silicasol through formation and drying after sufficient mixture. The solid sulfurizing agent reacts with hydrogen gas or hydrogen in semiwater gas at low temperature to stably generate high concentration H2S to completely meet the requirements of the sulfurizing technology of the Co-Mo catalysts, and has the advantages of safe and reliable use and good effect.

Description

Solid vulcanizing agnet for cobalt-molybdenum series catalyst vulcanization and preparation thereof
The present invention relates to solid sulfurizing agent that is specifically designed to the sulfuration of Co-Mo series carbon monoxide conversion catalyst and preparation method thereof.
Co-Mo is that transformation catalyst is good because of its low temperature active at present.Used widely at big or small synthesis ammonia plant, obtained considerable energy saving consumption reduction effect.During Co-Mo series catalysts product export is oxidation state, does not almost have shift activity, need earlier catalyst be vulcanized activation in the production equipment that uses factory, makes the cobalt of oxidation state and molybdenum be converted into sulphided state.Put into production then, high shift activity shows in the side.
Vulcanization process is, the semiwater gas under the uniform temperature by the container of vulcanizing agent is housed, produces the sulfuration unstripped gas that contains finite concentration hydrogen sulfide, and this gas is by the Co-Mo beds, progressively with CoO in the catalyst and MoO 3Be converted into CoS and MoS 2
What current C o-Mo series catalyst vulcanization the most generally used is carbon disulfide, this is a kind of inflammable and explosive low boiling (46.3 ℃ of boiling points, 105 ℃ of self-ignition points) organic solvent, poisonous, stench, skin and mucous membrane there is spread effect, in transportation, keeping with use very dangerously and inconvenient, often catch fire even accident such as blast.
Other still useful sulphur foams, troilite etc. add in the Gas-making Furnace, contain finite concentration H 2The gas of S comes the technology of sulphurized catalyst.But the shortcoming of this method is to be limited under the situation that full factory stops to use, and H 2S content is difficult for needing to regulate arbitrarily by sulfuration, can worsen the Gas-making Furnace operating mode, increases the weight of the equipment corrosion effect.
Aim of the present invention provides a kind of solid sulfurizing agent, and its transportation, keeping and use are all safe and reliable, uses technology simple and easy to do, with the catalyst activity height of its sulfuration.This solid sulfurizing agent has at a lower temperature the hydrogen reaction in (as long as 160 ℃ or a little more than 160 ℃) and the semiwater gas, stably produces high concentration H 2The performance of S meets the sulfuration process requirement fully, owing to generate H 2The reaction of S is exothermic reaction, does not need external heat source.
Solid sulfurizing agent constituent of the present invention comprises:
(1) elemental sulfur is or/and sulfur-containing compound sulphur (as ammonium polysulfide, sodium polysulfide, iron sulfide etc.), and containing the bright sulfur amount in vulcanizing agent weight is 10-75%, 40-60% more preferably,
(2) in the following additives one or more, it comprises:
A, organic additive comprise the high polymer that contains two keys, and vulcanizing agent, vulcanization accelerator etc. resemble butadiene-styrene rubber, butadiene rubber, natural rubber, acrylonitrile-butadiene rubber, carboxy styrene-butadiene rubber, carboxy terminatedpolybutadiene, carboxyl natural gum and their latex etc.; Resemble the alkylphenol monosulfide, alkyl phenol disulfide, the polysulfide of fat-based and PZ PZ, sodium diethyldithiocarbamate SDC, NB sodium dibutyl dithiocarbamate TP, zinc diethyl dithiocarbamate EZ, tetramethylthiuram disulfide TMTD, tetraethylthiuram disulfide TETD, curing di-penta methylene thiuram PTD, 2-benzothiazolyl mercaptan M, dibenzothiazyl disulfide DM, N-cyclohexyl-two-benzothiazole sulfenamide CZ, N, N '-di-n-butyl thiocarbamide DBTU, N, N '-thiambutosine CA.
B, inorganic additive comprise oxide or the sulfide of transition elements Fe, Co, Ni, Mo, W etc.,
The content of additive in vulcanizing agent is 1-30%, 5-20% more preferably,
(3) carrier is as Al 2O 3, SiO 2, ZnO, MgO, CaSO 4, the content of carriers such as diatomite in vulcanizing agent is 20-70%, 30-50% more preferably,
(4) gluing material, as waterglass, gypsum, Ludox,
Its content is the 4-30% of vulcanizing agent, best 10-18%, more than each composition weight percentage sum be 100%.
The preparation method of this solid sulfurizing agent is that the elemental sulfur of the required weight that will weigh up is or/and sulfur-containing compound and carrier, additive adopt mechanical shearing method or paddling process to mix, need to pulverize pulverize with pulverizer after, cross the 20-80 mesh sieve, adding an amount of gluing material mixes, be squeezed into the bar of diameter 4-12 millimeter, drying forming, length are nature fracture unequal length, or play the sheet moulding with tablet machine, sheet is changeable, be generally 5 * 5 millimeters cylindric.
Embodiment 1, take by weighing sublimed sulfur 64.4 grams, diatomite 20 grams, organic additive butadiene-styrene rubber (or butadiene rubber, acrylonitrile-butadiene rubber, carboxy styrene-butadiene rubber) 10.4 grams, TMTD or PTD0.2 gram behind the twin-roll machine mixing, are pulverized with pulverizer, cross 20 mesh sieves, add land plaster 5 gram mixings, break into 5 * 5 millimeters cylinder with tablet machine.
This solid sulfurizing agent discharges H 2The temperature of S and amount reach the active test in cobalt-molybdenum transformation catalyst sulfuration back, in microreactor, carry out, reaction tube diameter is 20 millimeters, and pipe is outer a heating and temperature controlling device, these solid sulfurizing agent 12 grams and 30 is restrained commercially available cobalt-molybdenum catalyst be respectively charged into and be numbered 1 #With 2 #In the reaction tube, the hydrogen-containing gas of feeding is a semiwater gas, 1 #The air velocity of the semiwater gas that pipe feeds can be controlled according to the needs of sulfuration, about about 25 ml/min, and the H that the reaction back produces 2S infiltrates and feeds 2 #In the semiwater gas of pipe, air velocity is controlled at 250 ml/min.When reaction tube temperature is raised to 170 ℃, begin to produce H 2S gas, control 1 #The flow of pipe semiwater gas makes H 2S concentration is entering 2 #Remain on 50 gram/rice before the reaction tube 3About, 2 #The process that pipe is pressed the transformation catalyst sulfuration heats up, and curing temperature generally is controlled at 250-450 ℃, time 8-10 hour.
Enter reaction tube 1 as long as control well #The flow of semiwater gas, under the required temperature and time condition of sulfuration, this solid sulfurizing agent can produce the H of desired concn all the time 2S gas, H 2The concentration of S can be controlled at 6-150 gram/rice 3, even in the bigger scope.
Transformation catalyst after the sulfuration of this solid sulfurizing agent is under 190 ℃, and when steam-to-gas ratio is 0.5, normal pressure, air speed are 500 -1The time, record interconversion rate and reach 90%.
Embodiment 2, take by weighing elemental sulfur 55 grams, Al 2O 320 grams, SiO 210 grams, MgO5 gram, ZnO5 gram, inorganic additive Fe 2O 31 gram, the CoO1 gram, the MoO3 gram behind pulverizer pulverizing mixing, is crossed 60 mesh sieves, adds 5 gram Ludox or waterglass again, and mixing in quick mixer is squeezed into diameter 4-12 millimeter strip, oven dry.
Measure this solid sulfurizing agent and begin to discharge H 2The temperature of S, H 2The burst size of S, the process conditions of sulfuration transformation catalyst, and the determinator of sulfuration rear catalyst activity and test procedure are with embodiment 1.
When reaction tube temperature rises to 202 ℃, begin to produce H 2S, according to the needs of sulfuration program, the flow of control semiwater gas can make solid sulfurizing agent produce the H of desired concn sustainedly and stably 2S gas, under 190 ℃, all the other conditions are during with example 1 through the transformation catalyst of this vulcanizing agent sulfuration, and the carbon monodixe conversion rate that records is 90%.
Embodiment 3, take by weighing ammonium polysulfide or sodium polysulfide 80 grams, Al 2O 320 grams, SiO 210 grams, inorganic additive FeS1 gram, NiS1 gram, MoS 21 gram, CoO1 gram, MoO 34 grams, land plaster 20 gram after mixing, breaks into 5 * 5 millimeters cylinder with tablet machine in quick mixer.
Method of testing and step are with embodiment 1.
When reaction tube temperature rises to 210 ℃, begin to produce H 2S gas, the flow of control semiwater gas, the sustainable H that stably produces desired concn of this solid sulfurizing agent 2S gas through the transformation catalyst of this vulcanizing agent sulfuration, under 190 ℃, when all the other conditions during with example 1, records and can make the interconversion rate of carbon monoxide reach 85%.
Embodiment 4, take by weighing elemental sulfur 15 grams, Heveatex 3 grams, and butadiene-styrene rubber or carboxy terminatedpolybutadiene 3 grams, TP or SDC, PZ0.03 gram TETD or PTD0.05 gram behind the twin-roll machine mixing, were pulverized 20 mesh sieves, again with Al 2O 330 grams, SiO 220 grams, MgO10 gram, ZnO10 gram, FeS2.5 gram, CoS2 gram, CoO0.5 gram, MoO 32 grams, Fe 2O 32 grams, land plaster 40 grams mix, and break into 5 * 5 millimeters cylinder with tablet machine.
Method of testing and step are with embodiment 1.
When reaction tube temperature rises to 180 ℃, begin to produce H 2S gas, the flow of control semiwater gas, the sustainable H that stably discharges desired concn of this solid sulfurizing agent 2S gas.
Through the transformation catalyst of this vulcanizing agent sulfuration, under 190 ℃, all the other conditions are during with example 1, and the carbon monodixe conversion rate that records is 83%.
Embodiment 5, take by weighing simple substance 75 grams, TMTD7.5 gram or CZ8 gram, diatomite 5 grams, Al 2O 35 grams, ZnO5 gram, SiO 22.5 gram, gypsum 10 grams mix with quick mixer, break into 5 * 5 millimeters cylinders with tablet machine again.
Method of testing and step are with embodiment 1.
When reaction tube temperature rises to 160 ℃, begin to produce H 2S, the flow of control semiwater gas, this solid sulfurizing agent can discharge the H of desired concn sustainedly and stably 2S gas.
Through the transformation catalyst of this vulcanizing agent sulfuration, under 190 ℃, all the other conditions are during with example 1, and the carbon monodixe conversion rate that records is 84%.
Embodiment 6, take by weighing elemental sulfur 10 grams, M or DM, DBTU1 gram, stearic acid 0.2 gram, ZnO5 gram, MgO5 gram, MgCo 35 grams, Al 2O 350 grams, SiO 223.8 gram, gypsum 5 grams mix with quick mixer, break into 5 * 5 millimeters cylinder again with tablet machine.
Method of testing and step are with embodiment 1,1 #The amount of solid sulfurizing agent can according to how many increases and decreases as one sees fit of vulcanizing agent sulfur content in the reaction tube.
When reaction tube temperature rises to 160 ℃, begin to produce H 2S, the flow of control semiwater gas, this solid sulfurizing agent can discharge the H of desired concn sustainedly and stably 2S gas.
Through the transformation catalyst of this vulcanizing agent sulfuration, under 190 ℃, all the other conditions are with example 1, and the interconversion rate of the carbon monoxide that records is 83%.

Claims (3)

1, a kind of solid sulfurizing agent that is used for the Co-Mo series catalyst vulcanization, it comprises:
(1) elemental sulfur is or/and ammonium polysulfide or sodium polysulfide, iron sulfide, and containing the bright sulfur amount in vulcanizing agent weight is 10-75%,
(2) in the following additives one or more, said additive includes organic additive: the high polymer that contains two keys, organic sulfurizing agent, vulcanization accelerator, resemble butadiene-styrene rubber, butadiene rubber, natural rubber, acrylonitrile-butadiene rubber, carboxy styrene-butadiene rubber, carboxy terminatedpolybutadiene, carboxyl natural gum and their latex etc., resemble the alkylphenol monosulfide, alkyl phenol disulfide, the polysulfide of fat-based and Methasam PZ, sodium diethyldithiocarbamate SDC, NB sodium dibutyl dithiocarbamate TP, zinc diethyl dithiocarbamate EZ, tetramethylthiuram disulfide TMTD, tetraethylthiuram disulfide TETD, curing di-penta methylene thiuram PTD, 2-benzothiazolyl mercaptan M, dibenzothiazyl disulfide DM, N cyclohexyl 2 benzothiazole sulfenamide CZ, N, N '-di-n-butyl thiocarbamide DBTU, N, N '-thiambutosine CA, inorganic additive: transition elements Fe, Co, Ni, Mo, the inorganic oxide of W etc. or sulfide, additive capacity is the 1-30% of vulcanizing agent weight
(3) carrier is as Al 2O 3, SiO 2, ZnO, MgO, CaSO 4, one or more mixtures in the diatomite, the carrier amount is the 20-70% of vulcanizing agent weight,
(4) gluing material, as waterglass, gypsum, one or more mixture in the Ludox, its amount is the 4-30% of vulcanizing agent weight,
More than each composition weight percentage sum be 100%.
2, solid sulfurizing agent as claimed in claim 1, it is characterized in that better composition counts by vulcanizing agent weight: elemental sulfur is or/and sulfur-bearing combined sulfur 40-60%
Additive 5-20%
Carrier 30 as one kind-50%
Gluing material 10-18%,
More than each composition weight percentage each 100%.
3, the method for preparing the described solid sulfurizing agent of claim 1, it is characterized in that elemental sulfur or sulfur-containing compound and additive, carrier adopts shearing method or paddling process to mix, and crosses the 20-80 mesh sieve, add an amount of gluing material mixing again, be squeezed into the bar of diameter 4-12 millimeter, oven dry, length is the nature breaking length, or play the sheet moulding with tablet machine, be generally 5 * 5 millimeters cylinders.
CN90104955A 1990-07-25 1990-07-25 Solid vulcanizing agnet for cobalt-molybdenum series catalyst vulcanization and preparation thereof Expired CN1018796B (en)

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CN90104955A CN1018796B (en) 1990-07-25 1990-07-25 Solid vulcanizing agnet for cobalt-molybdenum series catalyst vulcanization and preparation thereof

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CN90104955A CN1018796B (en) 1990-07-25 1990-07-25 Solid vulcanizing agnet for cobalt-molybdenum series catalyst vulcanization and preparation thereof

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CN1018796B true CN1018796B (en) 1992-10-28

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* Cited by examiner, † Cited by third party
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FR2689420B1 (en) * 1992-04-01 1994-06-17 Eurecat Europ Retrait Catalys PROCESS FOR PRESULFURIZING A HYDROCARBON PROCESSING CATALYST.
CN100363100C (en) * 2004-02-16 2008-01-23 杨典明 Desulfur catalyst
CN100360236C (en) * 2005-05-12 2008-01-09 中国石油化工股份有限公司 Treatment method before application of hydrogenation catalyst
CN100413587C (en) * 2005-05-12 2008-08-27 中国石油化工股份有限公司 Sulfurized type catalyst, and its prepn. method
CN101418236B (en) * 2007-10-26 2012-09-05 中国石油化工股份有限公司 Hydrocarbons hydrogenation method
CN104785273B (en) * 2015-03-30 2017-07-28 福州大学 A kind of Co Mo systems water gas converting catalyst and preparation method thereof
FI128221B (en) * 2015-04-27 2019-12-31 Metsae Fibre Oy Method for regenerating a catalyst used for producing polysulphide lye
JP6697287B2 (en) * 2016-03-02 2020-05-20 三菱日立パワーシステムズ株式会社 Catalyst for oxidation reaction of metallic mercury and reduction reaction of nitrogen oxide, and method for purifying exhaust gas
CN109569743B (en) * 2017-09-28 2021-11-30 中国石油天然气股份有限公司 Vulcanizing agent, and preparation method and application thereof
CN109261159B (en) * 2018-10-19 2021-04-30 青岛联信催化材料有限公司 Organic sulfur conversion type sulfur-tolerant shift catalyst and preparation method thereof
CN114681857B (en) * 2022-04-14 2023-02-28 呼和浩特市联合鼎盛固体废物处理有限公司 Comprehensive utilization method of catalyst

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