CN108043418A - A kind of preparation method of low cost high stability sulfur-resistant transformation catalyst - Google Patents
A kind of preparation method of low cost high stability sulfur-resistant transformation catalyst Download PDFInfo
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- CN108043418A CN108043418A CN201711192201.6A CN201711192201A CN108043418A CN 108043418 A CN108043418 A CN 108043418A CN 201711192201 A CN201711192201 A CN 201711192201A CN 108043418 A CN108043418 A CN 108043418A
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
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Abstract
The present invention relates to a kind of preparation methods of inexpensive high stability sulfur-resistant transformation catalyst, belong to catalyst technical field.The preparation method is to utilize waste and old Co Mo K/ γ Al2O3Sulfur-resistant transformation catalyst is roasted, natural cooling, is crushed, is then carried out hydro-thermal reaction, γ Al2O3Boehmite (AlOOH) is completely converted into, using existing method production active aluminum oxide carrier technique de- soon, prepares the fresh co-mo antisulphuric transforming catalyst of high stability.Make in waste and old co-mo antisulphuric transforming catalyst cobalt, molybdenum, potassium, aluminium oxide be able to all of, resource utilization rate reaches 100%, production cost is greatly reduced, and hydration-resisting stability, heat-resistant stability, intensity, the activity of catalyst are above the 11 type co-mo antisulphuric transforming catalysts of BASF Corp. of Germany K8 of industrial application.Effectively save resource, improves the utilization rate of limited resources, thoroughly solves waste and old co-mo antisulphuric transforming catalyst environmental pollution, realizes social sustainable development.
Description
Technical field
The present invention relates to a kind of preparation methods of inexpensive high stability sulfur-resistant transformation catalyst, belong to catalyst technology neck
Domain.
Background technology
The Co-Mo systems sulfur-resistant transformation catalyst in commercial Application mainly has two major classes at present：One kind for low pressure (<3.0MPa)
It is used under the conditions of low steam-gas ratio, using γ-Al2O3For carrier, such catalyst is mainly Co-Mo-K/ γ-Al2O3；It is another kind of
To be used under the conditions of high pressure (>=3.0MPa) high steam-to-gas ratio, using aluminum-spinel, such catalyst is mainly Co- for carrier
Mo/MgAl2O4Or Co-Mo/Mg-Al-Ti.For synthesizing the industries such as ammonia, synthesizing methanol.
China is " oil starvation, few gas, rich coal " in energy resource structure the characteristics of, and petroleum resources external dependence degree in 2016 has reached
65.4%, more than safe-guard line.Development of Coal base clean energy resource is an effective way for solving the problems, such as energy supply.Around hair
There is the Modern Coal-based Chemicals technology such as coal liquifaction, natural gas from coal, coal-to-olefin, coal-ethylene glycol again in the exhibition coal-based clean energy.
These new Modern Coal-based Chemical technologies have this technological requirement of adjusting C/Hratio, i.e. conversion process process, that is to say, that these
Project begun newly has conversion process, all can use co-mo antisulphuric transforming catalyst.
If need to consume 3 tons of CO co-mo antisulphuric transforming catalysts with every ten thousand tons of ammonia, every ten thousand tons of alcohol need to consume 2 tons of CO cobalt molybdenum resistant to sulfur
Transformation catalyst is estimated, is reported according to the international nitrogenous fertilizer of China in 2014, methanol conference, 2013 years whole nation synthesis hydrazine yields
6197.7 ten thousand tons, 35,850,000 tons of methanol output was calculated by 4 years service life, synthesized ammonia and methanol to cobalt molybdenum sulphur-resistant conversion
At least 6000 tons or more of the market Year's consumption of catalyst, along with plus new Modern Coal-based Chemical project (coal liquifaction, coal day
Right gas, coal-to-olefin, coal-ethylene glycol etc.) 4000 tons nearly to co-mo antisulphuric transforming catalyst Year's consumption, that is China
It is annual to there are 10000 tons of waste and old CO co-mo antisulphuric transforming catalysts to generate.
As environmental requirement is increasingly stringent, it is extremely urgent how to dispose these waste and old co-mo antisulphuric transforming catalysts, will
Waste and old co-mo antisulphuric transforming catalyst resource recycling not less than for a correct effective solution route, moreover produces new
The main raw material(s) of fresh co-mo antisulphuric transforming catalyst：The prices such as cobalt salt, molybdenum salt, aluminium oxide increase year by year, and 2017 compared with former years
Price is even more to be doubled, so by waste and old co-mo antisulphuric transforming catalyst recycling, remakes fresh high stability cobalt molybdenum
Sulfur-resistant transformation catalyst, can be greatly reduced production cost, and effectively save resource improves the utilization rate of limited resources, solves useless urge
Agent environmental pollution realizes social sustainable development, is contributed to build " amphitypy " society.
Patent CN 103553104A disclose a kind of recovery method of waste CO sulfur tolerant shift catalyst, more particularly to cobalt,
The recoverying and utilizing method of metal oxide in molybdenum system waste CO sulfur tolerant shift catalyst.The recovery method is by waste and old CO sulphur-resistant conversions
After catalyst crushes, by once roasting, leached after adding alkali after baking with hot water.After obtained filter residue acid adding dissolving, with alkali
Substep adjusts the pH value of solution, removes Fe (OH)3, separation Al (OH)3Afterwards up to the mixed liquor containing cobalt nitrate and potassium nitrate.The mixing
Liquid can be directly used for preparing new CO sulfur-resistant transformation catalysts.The filtrate that hot water leaches is with sour adjusted stepwise pH value, finally
Molybdic acid and potassium nitrate are can obtain, the metal in waste CO sulfur tolerant shift catalyst can be carried out fully separating time using the recovery method
It receives, the rate of recovery of cobalt reaches more than 85%, and the rate of recovery of molybdenum reaches more than 90%, and the rate of recovery is relatively low.Byproduct Al (OH)3Purity
Not enough, use value is little.Byproduct potassium nitrate also needs to concentrate, crystallizes, washs, drying, and entire technological process is long, and soda acid uses
Amount is big, and energy consumption is also big.
Patent CN 102950010A are reacted using the alkaline aqueous solution of potassium with waste and old co-mo antisulphuric transforming catalyst, by it
Contained molybdenum is converted into water-soluble powder body material, is directly used as preparing the active component raw material of sulfur-resistant transformation catalyst, prepares cobalt
Mo sulfur-tolerant shift catalyst product, molybdenum recovery is up to 90%.The patent simply will be in waste and old co-mo antisulphuric transforming catalyst
Molybdenum is used.
Patent CN 103769166B are related to a kind of recoverying and utilizing method of cobalt in waste and old co-mo antisulphuric transforming catalyst,
It is characterized in that after waste and old co-mo antisulphuric transforming catalyst is crushed, dissolves out cobalt therein with acid solution, filtrate is put into stirring after filtering
In device, using aluminum nitrate, magnesium nitrate and sodium carbonate as coprecipitator, precipitation reaction is carried out, is separated with centrifuge and washs to obtain
Forerunner's material containing cobalt, is used to prepare sulfur-resistant transformation catalyst.The patent is simply by cobalt in waste and old co-mo antisulphuric transforming catalyst
It is used.
Patent CN 1048196C are related to a kind of renovation process of cobalt-molybdenum type carbon-monoxide sulfur-resistance transformation catalyst, with the cobalt that gives up
Molybdenum type carbon-monoxide sulfur-resistance transformation catalyst is molten in ammonium hydroxide using the soluble-salt respectively containing cobalt, molybdenum and alkali metal as carrier
Again active constituent is impregnated in liquid or aqueous solution and prepares sulfur-resistant transformation catalyst.Patent CN 1079035C disclose a kind of waste and old
The renovation process of CO sulfur-resistant transformation catalysts, this method first crush waste and old sulfur-resistant transformation catalyst, then add in and intend thin water
The liquid peptizing agent such as the solids such as aluminium stone peptizing agent and nitric acid, is roasted, then molten with alkaline substance solution, Co-Mo active constituents
Liquid or Co-Mo- alkali metal compounds solution carry out activation process, drying or roasting.Above-mentioned patent is simply simply urged waste and old
Agent uses after directly using or crush, actually γ-Al in industrial waste co-mo antisulphuric transforming catalyst2O3, use three to five
After year, under certain temperature, pressure, water vapor condition, γ-Al2O3Phase structure has been partially converted into AlOOH object phases, if
Simply this dead catalyst directly or after crushing is used, the structural stability of the fresh catalyst prepared certainly will be caused to be deteriorated,
So that the hydration-resisting stability of fresh catalyst, heat-resistant stability, strength stability, activity stability are deteriorated.
The content of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of preparation sides of inexpensive high stability sulfur-resistant transformation catalyst
Method, it is characterised in that utilize waste and old Co-Mo-K/ γ-Al2O3Co-mo antisulphuric transforming catalyst, by it in 500 DEG C~550 DEG C roastings
2h is burnt, natural cooling is crushed to the mesh of 80 mesh~100, then carries out hydro-thermal reaction, γ-Al2O3It is completely converted into boehmite
(AlOOH), using existing method production active aluminum oxide carrier technique de- soon, the fresh cobalt molybdenum sulphur-resistant conversion of high stability is prepared
Catalyst.Cobalt, molybdenum, potassium, aluminium oxide in waste and old co-mo antisulphuric transforming catalyst is made to be able to all of resource utilization rate reaches
To 100%, production cost is greatly reduced, and hydration-resisting stability, heat-resistant stability, intensity, the activity of catalyst are above industry
The BASF Corp. of Germany K8-11 type co-mo antisulphuric transforming catalysts used.Effectively save resource improves the utilization of limited resources
Rate thoroughly solves waste and old co-mo antisulphuric transforming catalyst environmental pollution, realizes social sustainable development.
Existing method production active aluminum oxide carrier process flow chart de- soon is shown in Fig. 1.
As shown in Figure 1, raw material (α-gibbsite) is crushed to 325 mesh, thin α-three after drying in pulverizing process
Diaspore stops 0.1 second~l seconds in high temperature quick-dehydration device with 600~900 DEG C of hot gas in high turbulence thermal current
Shower roasting is carried out, generates transition state of alumina；Then through cyclone separator, fine powder addition water and auxiliary agent are made into viscous after separation
The green-ball for needing size dimension is made in mixture in disc type pelletizing forming machine, then impregnates in the hot water, it is not open close enter steam
Complete hydration process.Active aluminum oxide carrier most is made through high-temperature roasting afterwards.
The technical solution adopted by the present invention is：A kind of preparation method of low cost high stability sulfur-resistant transformation catalyst,
It is characterized by waste and old Co-Mo-K/ γ-Al2O3It is roasted 2h by co-mo antisulphuric transforming catalyst at 500 DEG C~550 DEG C,
Natural cooling is crushed to the mesh of 80 mesh~100, then carries out hydro-thermal reaction, γ-Al2O3Boehmite (AlOOH) is completely converted into,
After drying, 325 mesh are crushed in pulverizing process, thin boehmite (AlOOH) in high temperature quick-dehydration device, with
600 DEG C~900 DEG C hot gas stop in high turbulence thermal current carries out shower roasting for 0.1 second~l seconds, generation transition state oxidation
Aluminium；Then through cyclone separator, fine powder addition mass fraction is 60% magnesium acetate aqueous solution after separation, mass fraction is 50% second
Sour cobalt aqueous solution by volume 3：1 mixed aqueous solution being made into is adhesive, and 3~5mm of φ are made in disc type pelletizing forming machine
Green-ball or φ 4mm cylinder strips are made in banded extruder, be then immersed in mass fraction as in 10% wet chemical
Aquation, last activation procedure is through fresh sulfur-resistant transformation catalyst made of 450 DEG C~550 DEG C roastings.The catalyst cobalt oxide
(CoO mass fractions) content >=3.0%, molybdenum oxide (MoO3Mass fraction) content >=7.0%.
Above-mentioned carry out hydrothermal reaction condition is：
Temperature：300 DEG C~320 DEG C；
Heating rate：1℃/min
Pressure：10MPa~14MPa；
Steam-to-gas ratio：2.0~15.0
Gas medium：Water vapour, nitrogen；
Reaction time：96h~120h.
Beneficial effects of the present invention are：A kind of preparation method of low cost high stability sulfur-resistant transformation catalyst, feature
It is to utilize waste and old Co-Mo-K/ γ-Al2O3It is roasted 2h by co-mo antisulphuric transforming catalyst at 500 DEG C~550 DEG C, natural
Cooling is crushed to the mesh of 80 mesh~100, then carries out hydro-thermal reaction, γ-Al2O3Boehmite (AlOOH) is completely converted into, is utilized
Existing method production active aluminum oxide carrier technique de- soon, prepares the fresh co-mo antisulphuric transforming catalyst of high stability.Make to give up
Cobalt, molybdenum, potassium, aluminium oxide are able to all of resource utilization rate reaches 100%, life in old co-mo antisulphuric transforming catalyst
Production cost is greatly reduced, and hydration-resisting stability, heat-resistant stability, intensity, the activity of catalyst are above the Germany of industrial application
BASF AG K8-11 type co-mo antisulphuric transforming catalysts.Effectively save resource improves the utilization rate of limited resources, thoroughly solves
Waste and old co-mo antisulphuric transforming catalyst environmental pollution realizes social sustainable development.
Co-mo antisulphuric transforming catalyst hydration-resisting method for estimating stability：
Catalyst is under the conditions of certain temperature, liquid to steam ratio, pressure etc., after being kept for a period of time, with gas chromatograph point
Analyse carbon monoxide volume fraction in reactor import and export gas, calculate its CO conversion, and with water-fast procatalyst
CO conversion compared, the hydration-resisting of catalyst is characterized with the activity preservation rate of resistance to high water-gas ratio rear catalyst
Performance.
Co-mo antisulphuric transforming catalyst hydration-resisting stabilizing test device schematic diagram is shown in Fig. 3.
Co-mo antisulphuric transforming catalyst hydration-resisting performance test apparatus Specifeca tion speeification is shown in Table 1.
1 experimental rig main performance design parameter of table
| Project | Parameter |
| Specification/mm of reaction tube in reactor | φ38×3 |
| Isothermal section length/mm of reactor >= | 50 |
| Maximum working (operation) pressure (MWP)/MPa | 10.0 |
| Maximum operation (service) temperature/DEG C | 600 |
| Collimation (very poor value)/%≤ | 2 |
| Repdocutbility (very poor value)/%≤ | 3 |
If bar shaped, the sample that length is 3.5mm~4.0mm should be processed into；If spherical, should be processed into a diameter of
The sample of 4.0mm~5.0mm [with aperture is 4.0mm and the testing sieve of 5.0mm (according to R40/30 series in GB/T 6003.1)
Screening].It with the complete granularity samples of the tightly packed 100mL of 250mL graduated cylinders and weighs, acquires heap density, then weigh and be equivalent to
The sample of 30mL mass is spare.
One layer of stainless steel sieve is padded in the reaction bottom of the tube of reactor, the porcelain ball that clean granularity is 4mm~6mm will be handled
It is packed into reaction tube, and strikes reality, be filled to identified position when measuring isothermal region.Add one layer of stainless steel sieve on porcelain ball again,
The above-mentioned catalyst samples got ready are carefully poured into reaction tube, gently tap tube wall, makes catalyst bed filling close, and surveys
Its catalyst bed filling height is measured, then adds last layer stainless steel sieve, suitable granularity is packed into stainless steel sieve as 4mm
~6mm porcelain balls, gently strike reality, and after tightening reactor nut, reactor is accessed pilot system.Unstripped gas main valve is opened, to being
Be passed through unstripped gas in system, unstripped gas composition (with volume fraction) is carbon monoxide (45%~50%), carbon dioxide (3%~
5%), hydrogen sulfide (0.1%~0.5%), remaining is formed for hydrogen.And stablize under determination of activity pressure, close system disengaging
Mouth valve, pressure is dropped by less than 0.02MPa such as in 0.5h, then is considered as system sealing.Leak test is opened system after meeting the requirements and is gone out
Mouth valve exhaust, makes system be down to normal pressure.Temperature thermocouple is inserted into thermocouple sheath, its hot junction is made to be located at gas access catalysis
In agent bed at 5mm.
Unstripped gas is passed through into reactor, unstripped gas air speed is 750h-1, system pressure is normal pressure.Its elevated temperature cure operates
By the regulation of table 2.When temperature of reactor rises to 180 DEG C, start to be incorporated total sulfur into unstripped gas (with H2S is counted) it is 50g/Nm3~
70g/Nm3Vulcanizing agent, until temperature of reactor, from stopping during 420 DEG C of coolings with sulphur, vulcanization terminates.
2 vulcanisation operation condition of table
| Temperature range/DEG C | Heating rate/(DEG C/h) | Required time/h |
| Room temperature~250 | 60 | 4 |
| 250 | 0 | 6 |
| 250~350 | 50 | 2 |
| 350 | 0 | 4 |
| 350~420 | 50 | 1.5 |
| 420 | 0 | 2 |
| 420~350 | Temperature fall | — |
The measure of initial activity
Vaporizer, insulating tube are warming up to about 320 DEG C, control and adjust system pressure as 4.0MPa ± 0.02MPa, raw material
Gas air speed is 3000h-1±50h-1, vapor and feed gas volume ratio be 1.0 ± 0.02,350 DEG C ± 1 DEG C of temperature, stablize and simultaneously protect
After demonstrate,proving 4h, start the carbon monoxide volume fraction in analysis reactor disengaging gas, and calculate its CO conversion, so
It is measured once every 1.5h~2.0h afterwards, when continuously the very poor value of CO conversion no more than 1.0%, then can be tied three times
Beam initial activity is tested.
The measure of activity after water-fast
By temperature of reactor be down to 200 DEG C ± 1 DEG C, vapor and feed gas volume ratio be changed to 2.0 ± 0.02, control and protect
After holding 8h, then by temperature of reactor be raised to 350 DEG C ± 1 DEG C, vapor and feed gas volume ratio be changed to 1.0 ± 0.02, stablize 4h
Afterwards, start the carbon monoxide volume fraction in analysis reactor disengaging gas, and calculate its CO conversion, then often
It is measured once every 1.5h~2.0h.When continuously the very poor value of CO conversion no more than 1.0%, then can terminate resistance to three times
It is tested after water.Parking
Close unstripped gas main valve, system evacuation decompression, while the condensed water in relief condenser.When system is down to normal pressure
When, constant-flux pump is closed, stops water filling, final cutting system power supply.
Experimental data processing
Catalyst activity is calculated in terms of CO conversion E by formula (1)：
In formula (1)：
--- the numerical value of carbon monoxide volume fraction in unstripped gas is represented with %；
--- the numerical value of carbon monoxide volume fraction in conversion gas is represented with %.
Taking the arithmetic mean of instantaneous value of METHOD FOR CONTINUOUS DETERMINATION result three times, the very poor value of measurement result should be little three times as measurement result
In 1.0%.
Anti-hydration calculation formula
The anti-hydration E of catalyst0, calculated by formula (2)：
In formula (2)：
E1--- the numerical value of catalyst initial activity is represented with %；
E2--- the numerical value of activity after catalyst is water-fast is represented with %.
Result of calculation is represented to one decimal place.
Co-mo antisulphuric transforming catalyst heat-resistant stability evaluation method：
Catalyst is under the conditions of certain temperature, liquid to steam ratio, pressure etc., after being kept for a period of time, with gas chromatograph point
Analyse carbon monoxide volume fraction in reactor import and export gas, calculate its CO conversion, and with heat-resisting procatalyst
CO conversion compared, the heat resistance of catalyst is characterized with the activity preservation rate of heat-resisting rear catalyst.
Co-mo antisulphuric transforming catalyst heat-resistant stability test method is the same as co-mo antisulphuric transforming catalyst hydration-resisting stability
Test method.Water-fast rear active measure is simply changed to heat-resisting rear active measure.
Determination of activity condition is after heat-resisting：
By temperature of reactor be raised to 530 DEG C ± 1 DEG C, vapor and feed gas volume ratio be changed to 1.0 ± 0.02, control and protect
After holding 8h, then temperature of reactor is down to 350 DEG C ± 1 DEG C, after stablizing 4h, starts the oxygen in analysis reactor disengaging gas
Change carbon volume fraction, and calculate its CO conversion, then measured once every 1.5h~2.0h.When a continuous oxygen three times
Change the very poor value of efficiency of carbon con version no more than 1.0%, then can terminate heat-resisting rear experiment.
Heat resistance calculation formula
The heat resistance F of catalyst0, calculated by formula (3)：
In formula (3)：
F1--- the numerical value of catalyst initial activity is represented with %；
F2--- the numerical value of activity after catalyst is heat-resisting is represented with %.
Result of calculation is represented to one decimal place.
The assay method of co-mo antisulphuric transforming catalyst intensity：
It is performed by the measure of HG/T 2782-2011 chemical fertilizer catalyst particle anti-crushing powers.
The assay method of co-mo antisulphuric transforming catalyst cobalt molybdenum content：
It is performed by the measure of cobalt molybdenum content in HG/T 2781-2010 co surfer-resistant shift catalysts.
Co-mo antisulphuric transforming catalyst activity rating method：
It is performed by HG/T 4553-2013 co surfer-resistant shift catalyst mesohigh activity tests method.
Wherein activity rating condition：
Catalyst grain size：Bar shaped is processed into the sample that length is 3.5mm~4.0mm or φ 4.0mm~5.0mm are spherical；
Catalyst loading amount：30mL；
System pressure：(4.0±0.02)MPa；
Air speed：(3000±50)h-1；
Determination of activity temperature：(300±1)℃；
Steam-to-gas ratio：1.0±0.02.
Description of the drawings
Fig. 1 is existing method production active aluminum oxide carrier process flow chart de- soon；
Fig. 2 is the co-mo antisulphuric transforming catalyst production technological process of the present invention；
Fig. 3 is co-mo antisulphuric transforming catalyst hydration-resisting stabilizing test device schematic diagram.
1-1~1-2 --- mass flowmenter；1-3~1-4 --- wet gas flow meter；2——CS2Evaporator；
3 --- gas mixing bottle；4-1~4-2 --- reactor；5 --- vaporizer；6 --- constant-flux pump；7 --- gauge line；8-1~
8-2 --- condenser；9-1~9-2 --- water-sealed drainage bottle；10 --- gas chromatograph；11-1~11-2 --- devulcanizer；12-1~
12-2 --- alkali cleaning bottle；13 --- insulating tube
Specific embodiment：
Illustrate the present invention with specific embodiment below, enumerate these embodiments be in order to which the present invention is better described, and
The scope of the present invention is not restricted by the embodiments.
Embodiment 1
A kind of waste and old Co-Mo-K/ γ-Al2O3Sulfur-resistant transformation catalyst, through x-ray fluorescence analysis, consisting of quality point
Number (%)：Co (in terms of CoO)：1.5%, Mo are (with MoO3Meter)：8.6%, K2O：4.8%, S are (with SO2Meter)：9.2%, Al2O3：
75.9%.The waste and old co-mo antisulphuric transforming catalyst is roasted into 2h at 500 DEG C~550 DEG C, natural cooling is crushed to 100 mesh.It takes
The above-mentioned crushed materials of 100kg, be placed on maximum working (operation) pressure (MWP) 15.0MPa, 350 DEG C of maximum operation (service) temperature, in advance with nitrogen (>=
99.9%, with volume fraction) purge in clean 500L pressure vessels, 50kg deionized waters are then added in, are heated after sealing,
Control heating rate：1 DEG C/min, control temperature (300 ± 1) DEG C when pressure rises to 8.0MPa, is re-filled with nitrogen, keeps pressure
In (10.0 ± 0.1) MPa, temperature continues to control the 120h that holds time under (300 ± 1) DEG C, above-mentioned condition power.Then it is down to often
It is taken out after pressure, room temperature, after drying, is crushed to 325 mesh in pulverizing process, thin boehmite (AlOOH) is quick in high temperature
In dehydration device, stopped with 600 DEG C~900 DEG C hot gas in high turbulence thermal current 0.1 second~l seconds and carry out shower roasting,
Generate transition state of alumina；Then through cyclone separator, fine powder addition mass fraction is 60% magnesium acetate aqueous solution, matter after separation
Fraction is measured as 50% cobalt acetate aqueous solution by volume 3：1 mixed aqueous solution being made into is adhesive, in disc type pelletizing forming machine
In the green-ball of φ 3mm~5mm is made, be then immersed in mass fraction as aquation in 10% wet chemical, finally activate work
Sequence is through fresh co-mo antisulphuric transforming catalyst C1 made of 450 DEG C~550 DEG C roastings.
Embodiment 2
A kind of waste and old Co-Mo-K/ γ-Al2O3Sulfur-resistant transformation catalyst, through x-ray fluorescence analysis, consisting of quality point
Number (%)：Co (in terms of CoO)：1.5%, Mo are (with MoO3Meter)：8.6%, K2O：4.8%, S are (with SO2Meter)：9.2%, Al2O3：
75.9%.The waste and old co-mo antisulphuric transforming catalyst is roasted into 2h at 500 DEG C~550 DEG C, natural cooling is crushed to 100 mesh.It takes
The above-mentioned crushed materials of 100kg, be placed on maximum working (operation) pressure (MWP) 15.0MPa, 350 DEG C of maximum operation (service) temperature, in advance with nitrogen (>=
99.9%, with volume fraction) purge in clean 500L pressure vessels, 50kg deionized waters are then added in, are heated after sealing,
Control heating rate：1 DEG C/min, control temperature (300 ± 1) DEG C when pressure rises to 8.0MPa, is re-filled with nitrogen, keeps pressure
In (12.0 ± 0.1) MPa, temperature continues to control the 96h that holds time under (300 ± 1) DEG C, above-mentioned condition power.Then it is down to often
It is taken out after pressure, room temperature, after drying, is crushed to 325 mesh in pulverizing process, thin boehmite (AlOOH) is quick in high temperature
In dehydration device, stopped with 600 DEG C~900 DEG C hot gas in high turbulence thermal current 0.1 second~l seconds and carry out shower roasting,
Generate transition state of alumina；Then through cyclone separator, fine powder addition mass fraction is 60% magnesium acetate aqueous solution, matter after separation
Fraction is measured as 50% cobalt acetate aqueous solution by volume 3：1 mixed aqueous solution being made into is adhesive, in disc type pelletizing forming machine
In the green-ball of φ 3mm~5mm is made, be then immersed in mass fraction as aquation in 10% wet chemical, finally activate work
Sequence is through fresh co-mo antisulphuric transforming catalyst C2 made of 450 DEG C~550 DEG C roastings.
Embodiment 3
A kind of waste and old Co-Mo-K/ γ-Al2O3Sulfur-resistant transformation catalyst, through x-ray fluorescence analysis, consisting of quality point
Number (%)：Co (in terms of CoO)：1.5%, Mo are (with MoO3Meter)：8.6%, K2O：4.8%, S are (with SO2Meter)：9.2%, Al2O3：
75.9%.The waste and old co-mo antisulphuric transforming catalyst is roasted into 2h at 500 DEG C~550 DEG C, natural cooling is crushed to 100 mesh.It takes
The above-mentioned crushed materials of 100kg, be placed on maximum working (operation) pressure (MWP) 15.0MPa, 350 DEG C of maximum operation (service) temperature, in advance with nitrogen (>=
99.9%, with volume fraction) purge in clean 500L pressure vessels, 50kg deionized waters are then added in, are heated after sealing,
Control heating rate：1 DEG C/min, control temperature (320 ± 1) DEG C when pressure rises to 10.0MPa, is re-filled with nitrogen, keeps pressure
In (12.0 ± 0.1) MPa, temperature continues to control the 120h that holds time under (320 ± 1) DEG C, above-mentioned condition power.Then it is down to often
It is taken out after pressure, room temperature, after drying, is crushed to 325 mesh in pulverizing process, thin boehmite (AlOOH) is quick in high temperature
In dehydration device, stopped with 600~900 DEG C of hot gas in high turbulence thermal current and carry out within 0.1 second~l seconds shower roasting, it is raw
Into transition state of alumina；Then through cyclone separator, fine powder addition mass fraction is 60% magnesium acetate aqueous solution, quality after separation
Fraction is 50% cobalt acetate aqueous solution by volume 3：1 mixed aqueous solution being made into is adhesive, in disc type pelletizing forming machine
The green-ball of φ 3mm~5mm is made, is then immersed in mass fraction as aquation in 10% wet chemical, last activation procedure
Through fresh co-mo antisulphuric transforming catalyst C3 made of 450 DEG C~550 DEG C roastings.
Embodiment 4
A kind of waste and old Co-Mo-K/ γ-Al2O3Sulfur-resistant transformation catalyst, through x-ray fluorescence analysis, consisting of quality point
Number (%)：Co (in terms of CoO)：1.5%, Mo are (with MoO3Meter)：8.6%, K2O：4.8%, S are (with SO2Meter)：9.2%, Al2O3：
75.9%.The waste and old co-mo antisulphuric transforming catalyst is roasted into 2h at 500 DEG C~550 DEG C, natural cooling is crushed to 100 mesh.It takes
The above-mentioned crushed materials of 100kg, be placed on maximum working (operation) pressure (MWP) 15.0MPa, 350 DEG C of maximum operation (service) temperature, in advance with nitrogen (>=
99.9%, with volume fraction) purge in clean 500L pressure vessels, 50kg deionized waters are then added in, are heated after sealing,
Control heating rate：1 DEG C/min, control temperature (320 ± 1) DEG C when pressure rises to 10.0MPa, is re-filled with nitrogen, keeps pressure
In (14.0 ± 0.1) MPa, temperature continues to control the 96h that holds time under (320 ± 1) DEG C, above-mentioned condition power.Then it is down to often
It is taken out after pressure, room temperature, after drying, is crushed to 325 mesh in pulverizing process, thin boehmite (AlOOH) is quick in high temperature
In dehydration device, stopped with 600 DEG C~900 DEG C hot gas in high turbulence thermal current 0.1 second~l seconds and carry out shower roasting,
Generate transition state of alumina；Then through cyclone separator, fine powder addition mass fraction is 60% magnesium acetate aqueous solution, matter after separation
Fraction is measured as 50% cobalt acetate aqueous solution by volume 3：1 mixed aqueous solution being made into is adhesive, in disc type pelletizing forming machine
In the green-ball of φ 3mm~5mm is made, be then immersed in mass fraction as aquation in 10% wet chemical, finally activate work
Sequence is through fresh co-mo antisulphuric transforming catalyst C4 made of 450 DEG C~550 DEG C roastings.
Embodiment 5
A kind of waste and old Co-Mo-K/ γ-Al2O3Sulfur-resistant transformation catalyst, through x-ray fluorescence analysis, consisting of quality point
Number (%)：Co (in terms of CoO)：1.5%, Mo are (with MoO3Meter)：8.6%, K2O：4.8%, S are (with SO2Meter)：9.2%, Al2O3：
75.9%.The waste and old co-mo antisulphuric transforming catalyst is roasted into 2h at 500 DEG C~550 DEG C, natural cooling is crushed to 100 mesh.It takes
The above-mentioned crushed materials of 100kg, be placed on maximum working (operation) pressure (MWP) 15.0MPa, 350 DEG C of maximum operation (service) temperature, in advance with nitrogen (>=
99.9%, with volume fraction) purge in clean 500L pressure vessels, 50kg deionized waters are then added in, are heated after sealing,
Control heating rate：1 DEG C/min, control temperature (300 ± 1) DEG C when pressure rises to 8.0MPa, is re-filled with nitrogen, keeps pressure
In (10.0 ± 0.1) MPa, temperature continues to control the 120h that holds time under (300 ± 1) DEG C, above-mentioned condition power.Then it is down to often
It is taken out after pressure, room temperature, after drying, is crushed to 325 mesh in pulverizing process, thin boehmite (AlOOH) is quick in high temperature
In dehydration device, stopped with 600 DEG C~900 DEG C hot gas in high turbulence thermal current 0.1 second~l seconds and carry out shower roasting,
Generate transition state of alumina；Then through cyclone separator, fine powder addition mass fraction is 60% magnesium acetate aqueous solution, matter after separation
Fraction is measured as 50% cobalt acetate aqueous solution by volume 3：1 mixed aqueous solution being made into is adhesive, and φ is made in banded extruder
4mm cylinder strips are then immersed in mass fraction as aquation in 10% wet chemical, and last activation procedure is through 450 DEG C
Fresh co-mo antisulphuric transforming catalyst C5 made of~550 DEG C of roastings.
Embodiment 6
A kind of waste and old Co-Mo-K/ γ-Al2O3Sulfur-resistant transformation catalyst, through x-ray fluorescence analysis, consisting of quality point
Number (%)：Co (in terms of CoO)：1.5%, Mo are (with MoO3Meter)：8.6%, K2O：4.8%, S are (with SO2Meter)：9.2%, Al2O3：
75.9%.The waste and old co-mo antisulphuric transforming catalyst is roasted into 2h at 500 DEG C~550 DEG C, natural cooling is crushed to 100 mesh.It takes
The above-mentioned crushed materials of 100kg, be placed on maximum working (operation) pressure (MWP) 15.0MPa, 350 DEG C of maximum operation (service) temperature, in advance with nitrogen (>=
99.9%, with volume fraction) purge in clean 500L pressure vessels, 50kg deionized waters are then added in, are heated after sealing,
Control heating rate：1 DEG C/min, control temperature (300 ± 1) DEG C when pressure rises to 8.0MPa, is re-filled with nitrogen, keeps pressure
In (12.0 ± 0.1) MPa, temperature continues to control the 96h that holds time under (300 ± 1) DEG C, above-mentioned condition power.Then it is down to often
It is taken out after pressure, room temperature, after drying, is crushed to 325 mesh in pulverizing process, thin boehmite (AlOOH) is quick in high temperature
In dehydration device, stopped with 600 DEG C~900 DEG C hot gas in high turbulence thermal current 0.1 second~l seconds and carry out shower roasting,
Generate transition state of alumina；Then through cyclone separator, fine powder addition mass fraction is 60% magnesium acetate aqueous solution, matter after separation
Fraction is measured as 50% cobalt acetate aqueous solution by volume 3：1 mixed aqueous solution being made into is adhesive, and φ is made in banded extruder
4mm cylinder strips are then immersed in mass fraction as aquation in 10% wet chemical, and last activation procedure is through 450 DEG C
Fresh co-mo antisulphuric transforming catalyst C6 made of~550 DEG C of roastings.
Embodiment 7
A kind of waste and old Co-Mo-K/ γ-Al2O3Sulfur-resistant transformation catalyst, through x-ray fluorescence analysis, consisting of quality point
Number (%)：Co (in terms of CoO)：1.5%, Mo are (with MoO3Meter)：8.6%, K2O：4.8%, S are (with SO2Meter)：9.2%, Al2O3：
75.9%.The waste and old co-mo antisulphuric transforming catalyst is roasted into 2h at 500 DEG C~550 DEG C, natural cooling is crushed to 100 mesh.It takes
The above-mentioned crushed materials of 100kg, be placed on maximum working (operation) pressure (MWP) 15.0MPa, 350 DEG C of maximum operation (service) temperature, in advance with nitrogen (>=
99.9%, with volume fraction) purge in clean 500L pressure vessels, 50kg deionized waters are then added in, are heated after sealing,
Control heating rate：1 DEG C/min, control temperature (320 ± 1) DEG C when pressure rises to 10.0MPa, is re-filled with nitrogen, keeps pressure
In (12.0 ± 0.1) MPa, temperature continues to control the 120h that holds time under (320 ± 1) DEG C, above-mentioned condition power.Then it is down to often
It is taken out after pressure, room temperature, after drying, is crushed to 325 mesh in pulverizing process, thin boehmite (AlOOH) is quick in high temperature
In dehydration device, stopped with 600 DEG C~900 DEG C hot gas in high turbulence thermal current 0.1 second~l seconds and carry out shower roasting,
Generate transition state of alumina；Then through cyclone separator, fine powder addition mass fraction is 60% magnesium acetate aqueous solution, matter after separation
Fraction is measured as 50% cobalt acetate aqueous solution by volume 3：1 mixed aqueous solution being made into is adhesive, and φ is made in banded extruder
4mm cylinder strips are then immersed in mass fraction as aquation in 10% wet chemical, and last activation procedure is through 450 DEG C
Fresh co-mo antisulphuric transforming catalyst C7 made of~550 DEG C of roastings.
Embodiment 8
A kind of waste and old Co-Mo-K/ γ-Al2O3Sulfur-resistant transformation catalyst, through x-ray fluorescence analysis, consisting of quality point
Number (%)：Co (in terms of CoO)：1.5%, Mo are (with MoO3Meter)：8.6%, K2O：4.8%, S are (with SO2Meter)：9.2%, Al2O3：
75.9%.The waste and old co-mo antisulphuric transforming catalyst is roasted into 2h at 500 DEG C~550 DEG C, natural cooling is crushed to 100 mesh.It takes
The above-mentioned crushed materials of 100kg, be placed on maximum working (operation) pressure (MWP) 15.0MPa, 350 DEG C of maximum operation (service) temperature, in advance with nitrogen (>=
99.9%, with volume fraction) purge in clean 500L pressure vessels, 50kg deionized waters are then added in, are heated after sealing,
Control heating rate：1 DEG C/min, control temperature (320 ± 1) DEG C when pressure rises to 10.0MPa, is re-filled with nitrogen, keeps pressure
In (14.0 ± 0.1) MPa, temperature continues to control the 96h that holds time under (320 ± 1) DEG C, above-mentioned condition power.Then it is down to often
It is taken out after pressure, room temperature, after drying, is crushed to 325 mesh in pulverizing process, thin boehmite (AlOOH) is quick in high temperature
In dehydration device, stopped with 600 DEG C~900 DEG C hot gas in high turbulence thermal current 0.1 second~l seconds and carry out shower roasting,
Generate transition state of alumina；Then through cyclone separator, fine powder addition mass fraction is 60% magnesium acetate aqueous solution, matter after separation
Fraction is measured as 50% cobalt acetate aqueous solution by volume 3：1 mixed aqueous solution being made into is adhesive, and φ is made in banded extruder
4mm cylinder strips are then immersed in mass fraction as aquation in 10% wet chemical, and last activation procedure is through 450 DEG C
Fresh co-mo antisulphuric transforming catalyst C8 made of~550 DEG C of roastings.
Above-mentioned cobalt molybdenum resistant to sulfur is respectively adopted with commercially available K8-11 types co-mo antisulphuric transforming catalyst performance measurement in Examples 1 to 8
The assay method of transformation catalyst cobalt molybdenum content；The assay method of co-mo antisulphuric transforming catalyst intensity；Cobalt molybdenum sulphur-resistant conversion is urged
Agent hydration-resisting method for estimating stability；Co-mo antisulphuric transforming catalyst heat-resistant stability evaluation method；Cobalt molybdenum sulphur-resistant conversion is urged
Agent activity rating method is measured.Measurement result is shown in Table 3.
3 co-mo antisulphuric transforming catalyst cobalt molybdenum content of table, intensity, anti-hydration, heat resistance, determination of activity result
Note：K8-11 types co-mo antisulphuric transforming catalyst is BASF Corp. of Germany's industrial application product.
According to the Evaluation results of the catalyst of table 3, it can be seen that the cobalt molybdenum sulphur-resistant conversion prepared by the present invention is urged
Agent, intensity, anti-hydration, heat resistance, activity are superior to BASF Corp. of Germany K8-11 type co-mo antisulphuric transforming catalysts.
Claims (2)
1. a kind of preparation method of low cost high stability sulfur-resistant transformation catalyst, it is characterised in that utilize waste and old Co-Mo-K/
γ-Al2O3It is roasted 2h by co-mo antisulphuric transforming catalyst at 500 DEG C~550 DEG C, and natural cooling is crushed to 80 mesh~100
Then mesh carries out hydro-thermal reaction, γ-Al2O3Boehmite (AlOOH) is completely converted into, after drying, is broken in pulverizing process
325 mesh are broken to, thin boehmite (AlOOH) is in high temperature quick-dehydration device, with 600 DEG C~900 DEG C hot gas in height
It is stopped in turbulence thermal current 0.1 second~l seconds and carries out shower roasting, generate transition state of alumina；Then through cyclone separator, separation
Fine powder addition mass fraction is 60% magnesium acetate aqueous solution afterwards, mass fraction is 50% cobalt acetate aqueous solution by volume 3：1 matches somebody with somebody
Into mixed aqueous solution for adhesive, the green-ball of 3~5mm of φ is made in disc type pelletizing forming machine, or is made in banded extruder
φ 4mm cylinder strips are then immersed in mass fraction as aquation in 10% wet chemical, and last activation procedure is through 450
DEG C~fresh sulfur-resistant transformation catalyst made of 550 DEG C of roastings.
2. a kind of preparation method of inexpensive high stability sulfur-resistant transformation catalyst as described in claim 1, it is characterised in that
The carry out hydrothermal reaction condition:300 DEG C~320 DEG C of temperature；1 DEG C/min of heating rate；Pressure 10MPa~14MPa；Steam-to-gas ratio
2.0~15.0；Gas medium is water vapour and nitrogen；Reaction time 96h~120h.
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