CN101757941B - Novel Co-Mo sulfur-tolerant shift catalyst and preparation method thereof - Google Patents
Novel Co-Mo sulfur-tolerant shift catalyst and preparation method thereof Download PDFInfo
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- CN101757941B CN101757941B CN2009102565763A CN200910256576A CN101757941B CN 101757941 B CN101757941 B CN 101757941B CN 2009102565763 A CN2009102565763 A CN 2009102565763A CN 200910256576 A CN200910256576 A CN 200910256576A CN 101757941 B CN101757941 B CN 101757941B
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Abstract
The invention provides novel Co-Mo sulfur-tolerant shift catalyst which includes a carrier and active ingredients and is characterized in that the carrier is out-layer Mg-Al spinel of alumina base, and calculated by MgO, the Mg-Al spinel accounts for 3-20 % of the total weight of the carrier. Meanwhile, the invention provides a preparation method of the catalyst, which includes the following steps: evenly introducing dispersing agent-containing soluble magnesium salt or the mixture of soluble magnesium salt and aluminum salt to the alumina carrier through immersion method, curing through hot steam, drying and roasting for phase inversion to get out-layer Mg-Al spinel; and loading active ingredients on the out-layer Mg-Al spinel carrier through immersion method, curing through hot steam to fix the potassium, and roasting to resolve to get finished catalyst. The Co-Mo sulfur-tolerant shift catalyst not only has high activity, activity at low temperature and high temperature, high activity stability and wide activity temperature range, but also has high strength, high strength stability and high anti-hydration and anti-pulverization capabilities. The Co-Mo sulfur-tolerant shift catalyst can fit a wide range of water/gas ratio and a wide range of impurity content and is suitable for the technological process of conversion under medium/ high pressure and low temperature.
Description
Technical field
The present invention relates to a kind of Co-Mo sulfur-tolerant shift catalyst, specifically a kind of is the cobalt-molybdenum type carbon-monoxide sulfur-resistance transformation catalyst and preparation method thereof of carrier with the top layer magnesium aluminate spinel.
Background technology
In recent years, receive the restriction that energy general layout changes and influence, the newly-built nitrogen fertilizer plant of China multiselect is a raw material in order to coal or residual oil, is the large and medium-sized nitrogen fertilizer plant of raw material with light oil and be constructed and put into operation the beginning of the seventies, and also to become with the coal be raw material in reorganization and expansion.In these Design of device, consider that from aspects such as reduced investment, instant effects multiselect is with the 4.0MPa new technological flow that gas making, three sections sulphur-resistant conversions (middle change string is low to be become), methanation purifies that gasifies.Because the low temperature shift process pressure of this flow process is higher, temperature is lower; Catalyst will move under near 20 ℃ harsh conditions apart from dew-point temperature; Therefore the sulfur-resistant transformation catalyst that requires to be adapted to this technological process not only has higher low-temperature conversion active, also good stable property and anti-hydration will be arranged simultaneously.
It is that the sulfur-bearing that raw material generates contains CO gas with heavy oil, residual oil or coal that cobalt molybdenum sulphide catalyst is widely used in conversion, produces ammonia synthesis gas, hydrogen and oxo-synthesis gas.Co-Mo sulfur-tolerant shift catalyst is compared with Fe-Cr HTS transformation catalyst commonly used, uses wide temperature region, shift activity height, does not have the sulfur poisoning problem, therefore receives extensive attention, and many countries all research and develop.At present; The multiple sulfur-resistant transformation catalyst of succeeding in developing mainly contains two big types: one type is that the Co-Mo of carrier is a sulfur-resistant transformation catalyst for activated alumina; Comprise alkali metal, such catalyst low-temperature activity is good, to the broad that requires of sulfur content in the process gas; But the defective that has two aspects: alkali metal runs off easily under high temperature, high pressure and high steam-to-gas ratio condition on the one hand; The catalyst activity decline is serious, and carrier undergoes phase transition structural instability easily, even also possibly cause harmful effect to follow-up workshop section; In high pressure low temperature conversion process flow process, use on the other hand; Because conversion pressure is higher, temperature is lower; The hydration phase transformation takes place and causes specific surface to descend significantly in carrier inevitably, makes the irreversible inactivation of catalyst, and the stability of catalyst and hydration-resisting performance are relatively poor.Another kind of Co-Mo for the magnesium aluminate spinel carrier is a sulfur-resistant transformation catalyst, and carrier structure is stable, and intensity stabilization in the use is applicable to the conversion process that high temperature or high steam branch are depressed.
Chinese patent CN1003979, patent CN87107892 and U.S. Pat 3,850,840, patent US4 have reported with γ-Al in 153,580
2O
3Or with rare earth modified γ-Al
2O
3Be carrier, add the co-mo antisulphuric transforming catalyst of alkali metal promoter, the extensive use in industry at present of this type catalyst.The low temperature active of this type catalyst is high; But stability is poor with the hydration-resisting performance, in force down when using under the warm conversion process condition, carrier is generation hydration phase transformation inevitably; Cause that catalyst strength increases considerably, specific surface descends significantly, make catalyst produce irreversible inactivation.
U.S. Pat 3,529,935 have reported with MgO and Al
2O
3For carrier does not add alkali-metal como shift catalyst, temperature is active high in this type catalyst, and good stability suit to use than under the condition at high temperature or Gao Shui/gas, but low temperature active is poor, require water-gas that higher sulfur content is arranged, otherwise activity decay is serious.
Chinese patent CN1096494A, CN1429763A and CN148516A disclose with MgO, Al
2O
3And TiO
2Three kinds of hopcalites with add cement as carrier; Do not add alkali-metal como shift catalyst; Improved aforementioned deficiency of not adding the como shift catalyst of alkali metal promoter to a certain extent; But remain in tangible deficiency at stability, shift activity and aspects such as the low temperature active and the scope of application, combination property also needs further to improve.
Disclose a kind of sulfur-resistant transformation catalyst of hydration-resisting among the patent CN1241452A, earlier the carrier framework material has been carried out modification with the hydration-resisting auxiliary agent during preparation, with the compound of the major constituent titanium of carrier, soaked active component then again.
Disclose a kind of spherical high-pressure sulphur resistant translation catalyst among the Chinese patent CN101342491A, its carrier is a magnesium aluminate spinel, can only be applicable to the conversion process that high temperature or high steam branch are depressed, and forces down warm conversion process in can't being applied to.
Show that from the interrelated data retrieval that comprises Chinese patent not seeing as yet with the top layer magnesium aluminate spinel at present is the relevant report of the Co-Mo sulfur-tolerant shift catalyst of carrier.
Summary of the invention
Technical problem to be solved by this invention provides a kind of Novel Co-Mo sulfur-tolerant shift catalyst, solves stability and the problem of anti-hydration difference of the sulfur-resistant transformation catalyst of present alkali metal containing.
The present invention provides the preparation method of Novel Co-Mo sulfur-tolerant shift catalyst simultaneously, guarantees that magnesium salts or magnesium, the height of aluminium salt-mixture on alumina support evenly disperse, and reduces the potassium lost amount, prolongs catalyst service life.
A kind of Novel Co-Mo sulfur-tolerant shift catalyst of the present invention comprises carrier and active component, it is characterized in that said carrier is the top layer magnesium aluminate spinel of alumina base, and the content of magnesium aluminate spinel is counted 3～20% of carrier gross mass with MgO.
Wherein carrier is counted 75～90% of catalyst gross mass with metal oxide; Active component is an active component for the cobalt molybdenum of conventional alkali metal containing; By cobalt oxide or/and nickel oxide, molybdenum trioxide or/and tungstic acid and potassium oxide form; Cobalt is or/and nickel is counted 0.6～4% of catalyst gross mass with its oxide, and molybdenum is or/and tungsten is counted 5～15% of catalyst gross mass with it, and potassium is with K
2O counts 1～15% of catalyst gross mass.Preferably be made up of cobalt oxide, molybdenum trioxide and potash, cobalt is counted 0.6～4% of catalyst gross mass with CoO, and molybdenum is with MoO
3Count 5～15% of catalyst gross mass, potash is with K
2O counts 1～15% of catalyst gross mass.
The major technique characteristic of catalyst of the present invention is to have adopted the top layer magnesium aluminate spinel, has strengthened the stability and the hydration-resisting performance of catalyst, has widened the Application of Catalyst scope.The catalyst outward appearance is preferably sphere.
The preparation method who prepares Co-Mo sulfur-tolerant shift catalyst according to the invention is characterized in that comprising the steps:
C) preparation of top layer magnesium aluminate spinel carrier: use dispersant to prepare the mixed aqueous solution of certain density soluble magnesium saline solution or solubility magnesium salts and aluminium salt; Impregnated alumina,, roasting phase inversion dry through the superheated steam maintenance obtains top layer magnesium aluminate spinel carrier;
D) Preparation of catalysts: the activity of such catalysts set of dispense is processed maceration extract, and dipping top layer magnesium aluminate spinel carrier obtains the catalyst finished product through the solid potassium of superheated steam maintenance, roasting decomposition.
Wherein:
The said solubility magnesium salts of step a), aluminium salt are its nitrate, acetate or corresponding hydrate, when using solubility magnesium salts and aluminium salt mixed aqueous solution, and Mg in the mixed solution
2+: Al
3+Mol ratio=0.5.
The said dispersant of step a) is urea or surfactant; Its consumption is 0.05～5% of a catalyst gross mass, and wherein surfactant is a kind of or its composition of cetyl trimethyl amine, sodium cetanesulfonate, dodecyl sodium sulfate, ethylenediamine tetra-acetic acid, Tween 80, polyethylene glycol, polyvinyl alcohol, PPG.
The said aluminium oxide of step a) is γ-Al
2O
3, δ-Al
2O
3, θ-Al
2O
3, η-Al
2O
3, α-Al
2O
3In one or more mixture or their predecessor.Preferred γ-Al
2O
3
The said superheat steam temperature of step a) is 120 ℃, and maintenance drying time is 8～12 hours, and sintering temperature is 500～900 ℃, and constant temperature time is 3 hours.
The said superheat steam temperature of step b) is 120 ℃, and the solid potassium time of maintenance is 8～12 hours, and sintering temperature is 400～500 ℃, and the time is 3 hours.
Above-mentioned Preparation of catalysts method, solubility magnesium salts that uses infusion process on alumina support, evenly to introduce to contain dispersant or magnesium, aluminium salt-mixture, the thermal transition phase inversion is the top layer magnesium aluminate spinel; Use infusion process with active constituent loading in the top layer magnesium aluminate spinel carrier, through the solid potassium of high temperature handle, roasting prepares the CO sulfur-resistant transformation catalyst.Its key technology characteristics are: one, the use of dispersant guarantees that magnesium salts or magnesium, the height of aluminium salt-mixture on alumina support evenly disperse, the synthetic top layer of hot phase inversion magnesium aluminate spinel; Two, the solid potassium treatment process of catalyst, the potassium lost amount of handling rear catalyst through solid potassium obviously reduces, and prolongs the service life of catalyst.
The CO sulfur-resistant transformation catalyst of the present invention's preparation uses alumina support to be initial carrier; Through the structural stability that magnesium salts or magnesium, aluminium salt-mixture are evenly introduced carrier and magnesia-alumina spinel structure improves catalyst through the synthetic top layer of overheated phase inversion, prolong the service life of sulfur-resistant transformation catalyst.The content that we get MgO respectively is 3%, 8%, 12%, 15%, 20% carrier; Analyze with x-ray diffractometer; Can find out: the characteristic peak of all not finding MgO in the XRD figure of above-mentioned five carriers; Explain owing to adopted special dispersant, make magnesium salts or magnesium, aluminium salt-mixture on alumina support, highly evenly disperse; And the lattice paprmeter of [400] diffraction maximum is respectively in its XRD spectra
(γ-Al
2O
3The lattice paprmeter of [400] diffraction maximum do
MgAl
2O
4The lattice paprmeter of [400] diffraction maximum do
), clearly, on identical crystal face, the lattice paprmeter of above-mentioned five carriers is between γ-Al
2O
3And MgAl
2O
4Lattice paprmeter between, the angle of diffraction at characteristic of correspondence peak is between γ-Al
2O
3And MgAl
2O
4The angle of diffraction between (45.8 °～44.9 °).The content that MgO is described is in 3～20% scopes, at former Al
2O
3Formed MgAl on the top layer of carrier certain depth
2O
4Structure.
In the sulfur-resistant transformation catalyst system, it has been generally acknowledged that magnesium aluminate spinel (MgAl
2O
4) be optimum carrier, with γ-Al
2O
3Compare MgAl
2O
4Can not only improve the intensity of catalyst, can also make carrier have alkalescence, improve the shift activity of catalyst; And, MgAl
2O
4Carrier is more stable, and the variation of physical property and structure aspects can not take place in operation under industrial condition.The magnesium aluminate spinel carrier mainly adopts kneading method preparation, γ-Al at present
2O
3At high temperature calcine with magnesium compound, magnesium by the matrix top layer to body mutually in diffusion, replace the aluminium on the former spinelle tetrahedron, form MgAl by the stable spinel structure
2O
4The carrier of preparation has certain defective like this, and after the hydrothermal treatment consists, phase transformation in various degree takes place the magnesium aluminate spinel carrier, and this is because the particle size of formation carrier is big or roasting is incomplete, in carrier structure, stays free γ-Al
2O
3And have than strong absorptive MgO caused.The present invention adopts immersion process for preparing top layer magnesium aluminate spinel carrier.Use dispersant evenly to introduce solubility magnesium salts or soluble magnesium, aluminium salt-mixture, high-temperature roasting, Mg at alumina carrier surface
2+Can get into Al at an easy rate
3+And O
2-In the Al-O tetrahedral structure that forms, form stable " face-centered cubic " structure, generate the top layer magnesium aluminate spinel.Top layer magnesium aluminate spinel carrier has reduced free state MgO residual in the carrier structure to greatest extent, makes magnesium aluminate spinel constitute effective framework of carrier.The pore structure of top layer magnesium aluminate spinel carrier and surface acidity are by the alumina base decision that constitutes simultaneously.So top layer magnesium aluminate spinel carrier had both had Al
2O
3Suitable pore structure has the good structural stability of magnesium aluminate spinel again.
Sulfur-resistant transformation catalyst of the present invention in force down when using in the warm conversion process; The hydration phase transformation takes place in catalyst hardly; Have good stability and anti-hydration; And hydration phase transformation (seeing accompanying drawing 3) takes place when going up widely used transformation catalyst A and under same process conditions, using in industry at present inevitably.In addition, the technology that the present invention prepares catalyst is simple, can significantly reduce manufacturing cost.Catalyst of the present invention not only has high activity, high low temperature active, high-activity stable property and wide active temperature scope; And have high strength, high strength stability and high hydration-resisting, an anti-efflorescence ability; Can adapt to wide water/gas ratio and wide impurity level, be applicable to mesohigh low temperature shifting process flow process.
The performance evaluation of the sulfur-resistant transformation catalyst of gained of the present invention:
One, the catalyst anti-hydration is estimated
Utilize hydro-thermal device simulation industrial condition, investigate the hydration-resisting performance of catalyst carrier.Sample catalyst is put into reactor stainless steel pressure still; Add a certain amount of deionized water, sealing back heating, the control reactor temperature is at 200 ℃; Through the spontaneous steam pressure under this temperature to carrying out hydro-thermal reaction under the sample; Time is to the catalyst hydrothermal treatment consists after 4 hours, and the sample product carries out using XRD after the dried, detects its thing phase change.The quality of representing catalyst hydration-resisting performance with thing phase change amplitude size
Two, catalyst normal pressure intrinsic activity rating
Utilize the normal pressure micro-reactor,, test the catalyst normal pressure intrinsic activity of having eliminated the spreading factor influence away under the EQUILIBRIUM CONDITION.The little inverse spectral apparatus of normal pressure general flow chart is as shown in Figure 1.Employing is the unstripped gas of main component with CO, in reaction system, allocates an amount of water and CS into
2, CS
2Through γ-Al is housed
2O
3Hydrolysis reactor, generate H in 350 ℃ of following hydrolysis
2S gets into shift-converter, and reaction back tail gas separates through aqueous vapor, advances chromatography.
Appreciation condition: catalyst loading amount 0.3g; Pressure is normal pressure; Air speed 10000h
-1Water/gas 1.0; 285 ℃, 350 ℃, 450 ℃ of temperature; Unstripped gas is formed, CO 45-50% (v/v); CO
20-5% (v/v); H
2S 0.1-0.2% (v/v); Surplus is hydrogen.
CO interconversion rate computing formula is: X
CO=(Y
CO-Y
CO ')/[Y
CO(1+Y
CO ')] * 100%
Y
COThe molar fraction (butt) of-Reactor inlet gas CO
Y
CO 'The molar fraction of-reactor outlet gas CO (butt)
Three, catalyst pressurization activity rating
Pressurization activity rating device and flow process are as shown in Figure 2.This device is used to simulate industrial condition, under the certain pressure condition, measures the shift activity of " former granularity " catalyst under different condition, each item performance of overall merit catalyst.Reaction tube is the stainless steel tube of Φ 45 * 5mm, and there is the thermocouples tube of Φ 8 * 2mm in central authorities.Adopting Shandong two to change the preceding process gas of methanol plant conversion is unstripped gas, allocates an amount of H into
2S adds a certain amount of water according to the requirement of different WGRs, behind high-temperature gasification, gets into reaction tube with unstripped gas and carries out water gas shift reaction, reaction back tail gas chromatograph.
The pressurization appreciation condition is: catalyst loading amount: 50ml; Pressure 4.0MPa; Air speed 3000h
-1Water/gas 1.2; 285 ℃, 350 ℃, 450 ℃ of temperature; Unstripped gas is formed, CO 45-50% (v/v); CO
25-10% (v/v); H
2S>=0.2% (v/v); Surplus is hydrogen.
CO interconversion rate computing formula is: X
CO=(Y
CO-Y
CO ')/[Y
CO(1+Y
CO ')] * 100%
Y
COThe molar fraction (butt) of-Reactor inlet gas CO
Y
CO 'The molar fraction of-reactor outlet gas CO (butt)
Description of drawings
Fig. 1 is a normal pressure micro anti-evaluation device general flow chart;
Fig. 2 is the pressue device general flow chart;
Fig. 3 is an XRD spectra before and after catalyst C-01 and the experiment of industrial catalyst A hydro-thermal;
Fig. 4 is: the SEM figure before and after catalyst C-01 and the experiment of industrial catalyst A hydro-thermal.
Among the figure: 1. contain the H2S gas cylinder; 2. unstripped gas steel cylinder; 3. stop valve; 4. pressure maintaining valve; 5. spinner flowmeter; 6. triple valve; 7. threeway; 8. flow stabilizing valve; 9.CS2 bubbler; 10. water-bath saturator; 11. hydrolysis stove; 12. reactor; 13. steam condensation separator; 14. soap-foam flowmeter; 15. raw material gas purifying device; 16. pressure reducer; 17. blender; 18. Pressure gauge; 19. lockout valve; 20. heating furnace; 21. reaction tube; 22. thermocouples tube in the pipe; 23. condenser; 24. separator; 25. drain pump; 26. wet flow indicator; 27. vaporizer; 28. tank; 29. water measuring pump
The specific embodiment
Embodiment 1: spherical top layer magnesium aluminate spinel carrier synthetic
Buy industrial products ball-aluminium oxide carrier, its specific surface is 260m
2/ g, specific pore volume are 0.44ml/g, and intensity is 86N/, and water absorption rate 70%, bulk density are 0.60g/ml.With x-ray diffractometer carrier is carried out material phase analysis, the main component of this carrier is γ-Al
2O
3Get 200g magnesium nitrate crystal and be dissolved in the 50ml water, be heated to 60 ℃ and treat that the magnesium nitrate crystal all dissolves the back and adds 0.5g ethylenediamine tetra-acetic acid and 0.2g Tween 80, stirring and dissolving.With this mixed solution dipping 100 gram γ-Al
2O
3Carrier is put into Muffle furnace after using 120 ℃ superheated steam maintenance dried 12h, is warmed up to 800 ℃ according to the speed of 50 ℃/h, constant temperature 3h, and cooling obtains spherical top layer magnesium aluminate spinel carrier naturally.The composition of carrier: MgO:15%, Al
2O
3: 85%; Intensity: 138N/; Water absorption rate: 55%; With x-ray diffractometer carrier is carried out composition analysis, do not find to occur in the carrier characteristic peak of MgO; And its characteristic peak is between γ-Al
2O
3And MgAl
2O
4Characteristic peak between, prove γ-Al
2O
3The carrier top layer forms magnesia-alumina spinel structure.This bearer number is Z01.
Embodiment 2: spherical top layer magnesium aluminate spinel carrier synthetic
Use the alumina support among the embodiment 1, get 300g magnesium nitrate crystal and be dissolved in the 60ml water, be heated to 60 ℃ and treat that the magnesium nitrate crystal all dissolves the back and adds 3g urea, stirring and dissolving.With this mixed solution dipping 100 gram γ-Al
2O
3Carrier is put into Muffle furnace after using 120 ℃ the dry 12h of superheated steam maintenance, is warmed up to 800 ℃ according to the speed of 50 ℃/h, constant temperature 2h, and lowering the temperature naturally obtains spherical top layer magnesium aluminate spinel carrier.The composition of carrier: MgO:20%, Al
2O
3: 80%; Intensity: 126N/; Water absorption rate: 53%; With x-ray diffractometer carrier is carried out composition analysis, do not find to occur in the carrier characteristic peak of MgO; And its characteristic peak is between γ-Al
2O
3And MgAl
2O
4Characteristic peak between, prove γ-Al
2O
3The carrier top layer forms magnesia-alumina spinel structure.This bearer number is Z02.
Embodiment 3: spherical top layer magnesium aluminate spinel carrier synthetic
Buy the industrial products alumina support, its specific surface is 120m
2/ g, specific pore volume are 0.30ml/g, and intensity is 102N/, and water absorption rate 60%, bulk density are 0.70g/ml.With x-ray diffractometer carrier is carried out material phase analysis, the main component of this carrier is α-Al
2O
3, get 40g magnesium nitrate crystal and the 120g aluminum nitrate is dissolved in the 20ml water, be heated to 70 ℃ and treat that magnesium nitrate crystal, aluminum nitrate all dissolve the back and add 10g urea, stirring and dissolving.With this mixed solution dipping 100 gram alumina supports, put into Muffle furnace after using 130 ℃ superheated steam maintenance dried 12h, be warmed up to 900 ℃ according to the speed of 50 ℃/h, constant temperature 2h, lowering the temperature naturally obtains spherical top layer magnesium aluminate spinel carrier.The composition of carrier: MgO:3%, Al
2O
3: 95%; Intensity: 116N/; Water absorption rate: 59%; With x-ray diffractometer carrier is carried out composition analysis, do not find to occur in the carrier characteristic peak of MgO; And at γ-Al
2O
3And MgAl
2O
4Characteristic peak between a small peak appears, prove α-Al
2O
3The carrier top layer forms magnesia-alumina spinel structure.This bearer number is Z03.
Embodiment 4: spherical top layer magnesium aluminate spinel carrier synthetic
Use the γ-Al among the embodiment 1
2O
3Carrier is got 60g magnesium nitrate crystal and is dissolved in the 25ml water, is heated to 50 ℃ and treats that the magnesium nitrate crystal all dissolves the back and adds 0.05g PPG, stirring and dissolving.With this mixed solution incipient impregnation 100 gram γ-Al
2O
3Carrier is put into Muffle furnace after using 130 ℃ superheated steam maintenance dried 12h, is warmed up to 500 ℃ according to the speed of 50 ℃/h, constant temperature 4h, and cooling obtains spherical top layer magnesium aluminate spinel carrier naturally.The composition of carrier: MgO:8%, Al
2O
3: 92%; Intensity: 119N/; Water absorption rate: 55%; With x-ray diffractometer carrier is carried out composition analysis, do not find to occur in the carrier characteristic peak of MgO; And its characteristic peak is between γ-Al
2O
3And MgAl
2O
4Characteristic peak between, prove γ-Al
2O
3The carrier top layer forms magnesia-alumina spinel structure.This bearer number is Z04.
Embodiment 5: spherical top layer magnesium aluminate spinel carrier synthetic
Use the γ-Al among the embodiment 1
2O
3Carrier is got 70g magnesium nitrate crystal and is dissolved in the 25ml water, is heated to 60 ℃ and treats that the magnesium nitrate crystal all dissolves the back and adds 0.2g polyvinyl alcohol, stirring and dissolving.With this mixed solution dipping 100 gram γ-Al
2O
3Carrier is put into Muffle furnace after the drying, be warmed up to 600 ℃ according to the speed of 50 ℃/h, constant temperature 3h, and cooling obtains spherical top layer magnesium aluminate spinel carrier naturally.The composition of carrier: MgO:10%, Al
2O
3: 90%; Intensity: 121N/; Water absorption rate: 55%; With x-ray diffractometer carrier is carried out composition analysis, do not find to occur in the carrier characteristic peak of MgO; And its characteristic peak is between γ-Al
2O
3And MgAl
2O
4Characteristic peak between, prove γ-Al
2O
3The carrier top layer forms magnesia-alumina spinel structure.This bearer number is Z05.
Embodiment 6: spherical top layer magnesium aluminate spinel carrier synthetic
Use the γ-Al among the embodiment 1
2O
3Carrier is got 60g magnesium nitrate crystal and is dissolved in the 25ml water, is heated to 60 ℃ and treats that the magnesium nitrate crystal all dissolves the back and adds 0.3g cetyl sulfonic acid Trimethylamine, stirring and dissolving.With this mixed solution dipping 100 gram γ-Al
2O
3Carrier is put into Muffle furnace after the drying, be warmed up to 700 ℃ according to the speed of 50 ℃/h, constant temperature 3h, and cooling obtains spherical top layer magnesium aluminate spinel carrier naturally.The composition of carrier: MgO:10%, Al
2O
3: 90%; Intensity: 121N/; Water absorption rate: 55%; With x-ray diffractometer carrier is carried out composition analysis, do not find to occur in the carrier characteristic peak of MgO; And its characteristic peak is between γ-Al
2O
3And MgAl
2O
4Characteristic peak between, prove γ-Al
2O
3The carrier top layer forms magnesia-alumina spinel structure.This bearer number is Z06.
Embodiment 7: the preparation of sulfur-resistant transformation catalyst
Take by weighing ammonium tetramolybdate 12g and add in the 45ml ammoniacal liquor, heat of solution a little adds the 9g cobalt nitrate then and dissolves back adding 10g potash, and it is for use that solution clarification back adding 1ml ethylenediamine is mixed with co-impregnated solution.With this co-impregnated solution incipient impregnation 100g Z01 carrier, at the solid potassium 12h of 120 ℃ superheated steam maintenances, put into Muffle furnace afterwards, be warmed up to 450 ℃ according to the speed of 50 ℃/h, constant temperature 3h, lowering the temperature naturally obtains the catalyst finished product.Numbering C-01.
Comparing embodiment 8: the preparation of sulfur-resistant transformation catalyst
Take by weighing ammonium tetramolybdate 12g and add in the 45ml ammoniacal liquor, heat of solution a little adds the 9g cobalt nitrate then and dissolves back adding 10g potash, and it is for use that solution clarification back adding 1ml ethylenediamine is mixed with co-impregnated solution.With this co-impregnated solution incipient impregnation 100g Z01 carrier, put into Muffle furnace after dry, be warmed up to 450 ℃ according to the speed of 50 ℃/h, constant temperature 3h, lowering the temperature naturally obtains the catalyst finished product.Numbering C-01-1.
Catalyst is measured the result: according to normal catalyst physical and chemical performance assay method and above-mentioned anti-hydration evaluation method and activity rating method C-01 catalyst C-01-1 and the industrial catalyst A for preparing measured, measure the result and see table 1, table 2, table 3, table 4, accompanying drawing 3, accompanying drawing 4.
The chemical composition of table 1 catalyst and physico-chemical property
The eigentransformation of table 2 normal pressure is active
Table 3 " former granularity " the apparent shift activity that pressurizes
The solid potassium treatment process of table 4 is to the influence of the potassium lost amount of catalyst
Visible by table 1, table 2, table 3: Novel Co-Mo sulfur-tolerant shift catalyst C-01; The physical and chemical performance of its fresh sample and catalytic activity are suitable with industrial catalyst A; But the reservation eigentransformation activity of hydro-thermal experiment back sample obviously is superior to catalyst A; Explain that catalyst C-01 has better activity stability, thereby proof catalyst C-01 can be applied to commercial plant fully.Visible by table 4: catalyst C-01 is through special solid potassium treatment process, and the potassium lost amount of hydro-thermal experiment back sample reduces greatly.Visible by accompanying drawing 3: after the experiment of industrial catalyst A hydro-thermal, tangible hydration reaction has taken place, a large amount of hydration AlOOH occurred, essential variation has taken place in the structure of catalyst; And after being the catalyst C-01 hydro-thermal experiment of carrier with the top layer magnesium aluminate spinel, though very little AlOOH spectrum peak also occurred, the basic structure of catalyst does not change, and explains that the stability of catalyst of the present invention and hydration-resisting performance are good.Visible by accompanying drawing 4: two kinds of catalyst fresh sample are to be piled up by the fine particle that varies in size to form, and large and small duct has concurrently; And after the experiment of industrial catalyst A hydro-thermal, having many needle-likes or bar to separate out, the duct is all blocked by precipitate basically; And structure does not have too big variation basically before and after the experiment of catalyst C-01 hydro-thermal, and the no spicule in hydro-thermal experiment back occurs, and shows that equally the knot stability of catalyst C-01 is strong yet.And the production technology simple possible of catalyst has bigger economic benefit and social benefit.
Embodiment 9: the preparation of sulfur-resistant transformation catalyst
Take by weighing ammonium tetramolybdate 9g and add in the 45ml ammoniacal liquor, heat of solution a little adds the 18g cobalt nitrate then and dissolves back adding 2g potash, and it is for use that solution clarification back adding 1ml ethylenediamine is mixed with co-impregnated solution.With this co-impregnated solution incipient impregnation 100g Z05 carrier, at the solid potassium 12h of 120 ℃ superheated steam maintenances, put into Muffle furnace afterwards, be warmed up to 450 ℃ according to the speed of 50 ℃/h, constant temperature 3h, lowering the temperature naturally obtains the catalyst finished product.Be numbered C-02.Use pressurization activity rating device to detect, its CO conversion ratio is 90.8% (bed temperature is 250 ℃).
Embodiment 10: the preparation of sulfur-resistant transformation catalyst
Take by weighing ammonium paramolybdate 20g and add in the 45ml ammoniacal liquor, heat of solution a little adds the 6g cobalt nitrate then and dissolves back adding 26g potash, and it is for use that solution clarification back adding 1ml ethylenediamine is mixed with co-impregnated solution.With this co-impregnated solution incipient impregnation 100g Z04 carrier, at the solid potassium 12h of 120 ℃ superheated steam maintenances, put into Muffle furnace afterwards, be warmed up to 450 ℃ according to the speed of 50 ℃/h, constant temperature 3h, lowering the temperature naturally obtains the catalyst finished product.Be numbered C-03.Use pressurization activity rating device to detect, its CO conversion ratio is 96.2% (bed temperature is 250 ℃).
Embodiment 11: the preparation of sulfur-resistant transformation catalyst
Take by weighing ammonium tetramolybdate 15g and add in the 45ml ammoniacal liquor, heat of solution a little adds the 4g cobalt nitrate then and dissolves back adding 10g potash, and it is for use that solution clarification back adding 1ml ethylenediamine is mixed with co-impregnated solution.With this co-impregnated solution incipient impregnation 100g Z02 carrier, at the solid potassium 12h of 150 ℃ superheated steam maintenances, put into Muffle furnace afterwards, be warmed up to 450 ℃ according to the speed of 50 ℃/h, constant temperature 3h, lowering the temperature naturally obtains the catalyst finished product.Be numbered C-04.Use pressurization activity rating device to detect, its CO conversion ratio is 96.1% (bed temperature is 250 ℃).
Embodiment 12: the preparation of sulfur-resistant transformation catalyst
Take by weighing ammonium paramolybdate 18g and add in the 45ml ammoniacal liquor, heat of solution a little adds the 13g cobalt nitrate then and dissolves back adding 15g potash, and it is for use that solution clarification back adding 1ml ethylenediamine is mixed with co-impregnated solution.With this co-impregnated solution incipient impregnation 100gZ01 carrier, at the solid potassium 12h of 120 ℃ superheated steam maintenances, put into Muffle furnace afterwards, be warmed up to 450 ℃ according to the speed of 50 ℃/h, constant temperature 3h, lowering the temperature naturally obtains the catalyst finished product.Be numbered C-05.Use pressurization activity rating device to detect, its CO conversion ratio is 95.6% (bed temperature is 250 ℃).
Embodiment 13: the preparation of sulfur-resistant transformation catalyst
Take by weighing ammonium tetramolybdate 6g and add in the 45ml ammoniacal liquor, heat of solution a little adds the 16g cobalt nitrate then and dissolves back adding 12g potash, and it is for use that solution clarification back adding 1ml ethylenediamine is mixed with co-impregnated solution.With this co-impregnated solution incipient impregnation 100g Z01 carrier, at the solid potassium 12h of 130 ℃ superheated steam maintenances, put into Muffle furnace afterwards, be warmed up to 450 ℃ according to the speed of 50 ℃/h, constant temperature 3h, lowering the temperature naturally obtains the catalyst finished product.Be numbered C-06.Use pressurization activity rating device to detect, its CO conversion ratio is 94.5% (bed temperature is 250 ℃).
Embodiment 14: the preparation of sulfur-resistant transformation catalyst
Take by weighing ammonium tetramolybdate 15g and add in the 45ml ammoniacal liquor, heat of solution a little adds the 18g cobalt nitrate then and dissolves back adding 4g potash, and it is for use that solution clarification back adding 1ml ethylenediamine is mixed with co-impregnated solution.Cross volume dipping 100gZ05 carrier with this co-impregnated solution,, put into Muffle furnace afterwards, be warmed up to 450 ℃ according to the speed of 50 ℃/h at the solid potassium 12h of 120 ℃ superheated steam maintenances, constant temperature 3h, lowering the temperature naturally obtains the catalyst finished product.Be numbered C-07.Use pressurization activity rating device to detect, its CO conversion ratio is 94.9% (bed temperature is 250 ℃).
Embodiment 15: the preparation of sulfur-resistant transformation catalyst
Take by weighing ammonium tetramolybdate 12g and add in the 45ml ammoniacal liquor, heat of solution a little adds the 9g cobalt nitrate then and dissolves back adding 10g potash, and it is for use that solution clarification back adding 1ml ethylenediamine is mixed with co-impregnated solution.With this co-impregnated solution incipient impregnation 100g Z06 carrier, at the solid potassium 12h of 120 ℃ superheated steam maintenances, put into Muffle furnace afterwards, be warmed up to 450 ℃ according to the speed of 50 ℃/h, constant temperature 3h, lowering the temperature naturally obtains the catalyst finished product.Numbering C-08.Use pressurization activity rating device to detect, its CO conversion ratio is 96.7% (bed temperature is 250 ℃).
Embodiment 16: the preparation of sulfur-resistant transformation catalyst
Take by weighing ammonium tetramolybdate 12g and add in the 45ml ammoniacal liquor, heat of solution a little adds the 9g cobalt nitrate then and dissolves back adding 10g potash, and it is for use that solution clarification back adding 1ml ethylenediamine is mixed with co-impregnated solution.With this co-impregnated solution incipient impregnation 100g Z03 carrier, at the solid potassium 12h of 120 ℃ superheated steam maintenances, put into Muffle furnace afterwards, be warmed up to 450 ℃ according to the speed of 50 ℃/h, constant temperature 3h, lowering the temperature naturally obtains the catalyst finished product.Numbering C-09.Use pressurization activity rating device to detect, its CO conversion ratio is 89.6% (bed temperature is 250 ℃).
Claims (2)
1. a Co-Mo sulfur-tolerant shift catalyst comprises carrier and active component, it is characterized in that:
Said carrier is the top layer magnesium aluminate spinel of alumina base, and the content of magnesium aluminate spinel is counted 3～20% of carrier gross mass with MgO; Carrier is counted 75～90% of catalyst gross mass with metal oxide;
Active component is that cobalt oxide, molybdenum trioxide and potash are formed, and cobalt is counted 0.6～4% of catalyst gross mass with its oxide, and molybdenum is counted 5～15% of catalyst gross mass with its oxide, and potassium is with K
2O counts 1～15% of catalyst gross mass;
Its preparation method comprises the steps:
A. the preparation of the top layer magnesium aluminate spinel carrier of alumina base: use dispersant to prepare the mixed aqueous solution of certain density soluble magnesium saline solution or solubility magnesium salts and aluminium salt; Impregnated alumina is through the top layer magnesium aluminate spinel carrier that the superheated steam maintenance is dry, the roasting phase inversion obtains alumina base; Wherein
The described dispersant of step a is urea or surfactant; Its consumption is 0.05～5% of a catalyst gross mass, and said surfactant is selected a kind of or its composition of sodium cetanesulfonate, dodecyl sodium sulfate, Tween 80, polyethylene glycol, polyvinyl alcohol, PPG;
The said solubility magnesium salts of step a, aluminium salt are its nitrate or acetate; When using solubility magnesium salts and aluminium salt mixed aqueous solution, Mg in the mixed solution
2+: Al
3+Mol ratio=0.5;
The described aluminium oxide of step a is γ-Al
2O
3, δ-Al
2O
3, θ-Al
2O
3, η-Al
2O
3, α-Al
2O
3In one or more;
The described superheat steam temperature of step a is 120 ℃, and maintenance drying time is 8～12 hours, and sintering temperature is 500～900 ℃, and constant temperature time is 3 hours;
B. Preparation of catalysts: the activity of such catalysts set of dispense is processed maceration extract, and the top layer magnesium aluminate spinel carrier that oxide impregnation is aluminium base decomposes through the solid potassium of superheated steam maintenance, roasting and to obtain the catalyst finished product;
The said superheat steam temperature of step b is 120 ℃, and the solid potassium time of maintenance is 8～12 hours, and sintering temperature is 400～500 ℃, and the time is 3 hours.
2. Co-Mo sulfur-tolerant shift catalyst according to claim 1 is characterized in that the catalyst outward appearance is for spherical.
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| CN112090435B (en) * | 2019-06-18 | 2023-01-03 | 国家能源投资集团有限责任公司 | Cobalt-molybdenum-based sulfur-tolerant shift catalyst and preparation method and application thereof |
| CN112742429A (en) * | 2019-10-29 | 2021-05-04 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
| CN113880124A (en) * | 2020-07-01 | 2022-01-04 | 中国石油天然气股份有限公司 | Method for preparing magnesium aluminate spinel by impregnation |
| CN114471589A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Catalyst, method for sulfur-tolerant shift catalytic reaction and method for preparing methane |
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