CN105562006A - High-precision desulfurization catalyst and preparation process thereof - Google Patents
High-precision desulfurization catalyst and preparation process thereof Download PDFInfo
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Abstract
The present invention relates to a high-precision desulfurization catalyst and a preparation process thereof, wherein the raw materials comprise, by weight, metal salts (calculated as the weight of the oxide) such as 42-47 parts of CuO, 42-47 parts of ZnO, 5-12 parts of Al2O3, and 0.5-5 parts of ZrO2, 3-5 parts of a lubricant, 100-198 parts of a precipitation agent, and 5-15 parts of water, wherein a molar ratio of copper to zinc is 1:1. According to the present invention, the catalyst has a wide use temperature and can be used at a temperature from the room temperature to 450 DEG C; the breakthrough sulfur capacity at a temperature of 250 DEG C can achieve 33%; within a temperature range from a room temperature to 450 DEG C, when the raw material sulfur content is less than or equal to 0.5 ppm, it can be ensured that the desulfurization degree achieves 5 ppb or less; and the catalyst has the long service life and can be used for a long during the normal use, such that the user time and the operation cost are saved, and the accident of the damage on the catalyst due to the incorrect user operation is avoided.
Description
Technical field
The present invention relates to a kind of fine desulfurizing technology and catalyst thereof, be specifically related to a kind of high accuracy desulphurization catalyst and preparation technology thereof.
Background technology
In the technical process of hydrocarbon raw material steam-reforming hydrogen making, ammonia synthesis gas, oxo-synthesis gas, the sulfur content in raw material should reduce the service life extending subsequent transformation catalyst as far as possible.The sulfur poisoning of reforming catalyst is relevant to reaction bed temperature, and when 800 DEG C, 5ppm sulphur just can cause reforming catalyst poisoning, and when 500 DEG C, 0.01ppm can cause poisoning.Usual use Zinc oxide catalytic removes hydrogen sulfide and multiple organic sulfur (except thiophene-based), and desulfurization precision reaches 0.1ppm.But because the process conditions of some device limit, the minimum sulfur content needed for cannot being obtained by Zinc oxide catalytic, in the case, needs to use smart catalyst.Along with the development of hydrocarbon steam conversion technique and catalyst technology, unit scale maximizes, energy-saving becomes trend, pre reforming Process and catalyst widely use, and pre-converting catalyst is generally used in 325 ~ 650 DEG C of temperature ranges, belong to the non-renewable region of sulfur poisoning (temperature more than 700 DEG C, the slight sulfur poisoning recovery of reforming catalyst).For guaranteeing the long-term operation of the high activity of pre-converting catalyst, activity stability and reforming catalyst, World Catalyst manufacturer develops high performance smart catalyst (finalpurificationcatalyst).As Denmark HaldorTops φ e develops ST-101 catalyst, copper zinc system, serviceability temperature 80 ~ 360 DEG C, Sulfur capacity 1 ~ 18wt%, during feed sulphur content 0.1ppm, guarantees that desulfurization is to 5ppb; Britain JohnsonMatthey develops PURASPEC
jM2084, copper zinc system.
Cu-series catalyst, as copper zinc-aluminium system, copper zinc system, copper zinc-manganese system, serviceability temperature is lower, and generally at 200-360 DEG C, in order to avoid shot copper footpath is magnified under high temperature, catalytic activity declines.When using as high accuracy desulphurization catalyst, for making full use of the Sulfur capacity of front system oxidation zinc, temperature of charge generally can reach 380 DEG C or higher, therefore pursues the high-temperature stability of catalyst.
Summary of the invention
The object of this invention is to provide a kind of high accuracy desulphurization catalyst and preparation technology thereof, catalyst serviceability temperature is wide, and the working sulfur capacity 250 DEG C time is high, and desulfurization degree is high.Save time and the operating cost of user, avoid the accident of the improper damage catalyst of user operation.
A kind of high accuracy desulphurization catalyst of the present invention, with weight parts, raw material is composed as follows:
Metallic salt, by oxide weight: CuO42-47 part, ZnO42-47 part, Al
2o
35-12 part; ZrO
20.5-5 part; Wherein, the molar ratio of copper zinc is 1:1;
Lubricant 3-5 part;
Precipitating reagent 100-198 part;
Water 5-15 part.
Precipitating reagent can make the salts solution of copper, zinc, aluminium, zirconium be reacted into sediment.For ensureing to precipitate completely, precipitating reagent is preferably excessive, controls precipitating reagent excessive 10% ~ 25%.
Lubricant is any one or a few in graphite, paraffin or stearate;
Precipitating reagent be in NaOH or sodium carbonate any one or multiple.
The salts solution of copper, zinc, aluminium, zirconium is nitrate, preferred copper nitrate, zinc nitrate or aluminum nitrate.
The preparation method of high accuracy desulphurization catalyst, preparation process is: by copper, zinc, aluminium, be heated to 45-90 DEG C after the salting liquid of zirconium mixes mutually and obtain solution A, precipitating reagent is mixed with solution, obtain solution B, under 0.20-0.42rad/s mixing speed, solution A is added drop-wise in solution B and carries out precipitation reaction, then carry out aging to material, after aging end, material is washed, dry, mixed material is obtained after roasting kinetics, lubricant is added at mixed material, mix, obtained semi-finished product catalyst, add water in semi-finished product catalyst, compressing.
2-5 part lubricant is added in every 100 parts of mixed materials.
The metal ion molar concentration of solution A is 1.0-4.0mol/L, preferred 1.0-1.5mol/L.
The metal ion molar concentration of solution B is 0.5-3.0mol/L, preferred 1.0-1.5mol/L.
The solution temperature of solution A is than solution B solution temperature height 2-5 DEG C.
The solution temperature of solution A is 45-90 DEG C, is preferably 70-85 DEG C; The solution temperature of solution B is 45-90 DEG C, is preferably 70-85 DEG C.Solution A, solution B keep certain temperature, are conducive to the uniform sediment of acquisition state, and have material impact to the copper grain size of finished catalyst.
Mixing speed is 0.20-0.42rad/s, the preferred 0.29-0.36rad/s of mixing speed.If mixing speed is too fast or excessively slow, the copper grain size of sedimentary uniformity and finished catalyst will be affected.
The speed that solution A is added drop-wise to solution B is 0.1-0.4mol/min, preferred 0.15-0.25mol/min.If rate of addition is too fast or excessively slow, the copper grain size of sedimentary uniformity and finished catalyst will be affected.
Ultrasonic frequency is 45-50KHz, and the sound intensity is generally 0.5 ~ 1.5W/cm
2.Preferred ultrasonic frequency is 50KHz, sound intensity 1W/cm
2.Ultrasonic frequency is higher, and ultrasonic wave is easily decayed, and frequency too low noise is too large.When precipitate and aging time, for making deposit seed tiny as much as possible, guarantee sedimentary uniformity, open ultrasonic wave slurries are shaken, assist paddle improve stirring capacity, pulverizing sediment, make it trickleer, when closing ultrasonic wave after aging end.
Be connected by flange between supersonic generator with ultrasonic wave distributor, ultrasonic wave distributor is positioned at bottom reactor.
Ultrasonic wave distributor used is arranged on bottom reactor, disperses ultrasonic wave by the curved surface bottom reactor.
Copper, zinc, aluminium, zirconium compounds produce precipitation by the effect of the acidity of reactant and alkaline two aspects, because of but precipitate simultaneously, sediment is a kind of black mixture.
Precipitation reaction terminates, and slurry pH value is 8.5-9.
Aging temperature is 45-90 DEG C, and ageing time is 1-12 hour.
Temperature during aging, precipitation reaction is identical with the temperature of solution B.
Wash temperature 45-90 DEG C, is preferably 70-85 DEG C.For the purpose of slurry amount, the 50-600 of catalyst quality doubly, is preferably 200-250 doubly.After the aging end of slurries, immediately filtration washing is carried out to slurries.In order to avoid slurries ageing time is long, grain growth affects catalyst activity too much; Or slurry temperature reduces, and causes detersive efficiency to decline, waste deionized water and time.
Baking temperature is 120-125 DEG C.
Sediment sintering temperature is 600-650 DEG C, and roasting time is 1-6h, is preferably 2-4h.
Water in the present invention is deionized water.
Catalyst bulk density 0.80-0.85kg/L of the present invention, cupric oxide particle diameter is less than 8nm, and the hole of 90% or more is aperture (≤10nm), and zinc oxide particle diameter is between 10-20nm.
High accuracy desulphurization catalyst of the present invention is copper zinc System Catalyst, become cylindrical shape, bulk density 0.80-0.85kg/L, bulk density is far below current business-like copper zinc, CuZnAl catalyst, catalyst of the present invention also keeps higher intensity simultaneously, side pressure strength can reach more than 300N/cm, is enough to guarantee industrial application intensity, and 450 DEG C of stable performance under high temperature.
In use, active constituent copper has 2 kinds of forms to catalyst of the present invention: oxidized and reduced.
The gas medium of desulfurization is distinguished as required, and the gas of if desired desulfurization contains reproducibility component, as hydrogen, then catalyst needs prereduction before use, if desired the gas of desulfurization is not containing reproducibility component, then catalyst uses oxidation state or reduction-state, respectively for differential responses technique.
When the sulfide containing material for the treatment of not hydrogen, catalyst of the present invention adopts oxidation state to complete the catalyst of desulfurizing and purifying and reduction-state.
When the sulfide containing material for the treatment of hydrogen, the catalyst of reduction-state must be used.
Use high accuracy desulphurization catalyst of the present invention, omit pipeline complicated in old process and valve, reduce personnel labor intensity, conventional catalyst is loaded at desulfurizer A, as Zn, Fe, Mn series catalysts, load conventional catalyst and high accuracy desulphurization catalyst of the present invention at desulfurizer B, filling ratio is conventional catalyst: high accuracy desulphurization catalyst=1:1 ~ 3:1.
In catalyst use procedure, operating personnel only need the purge cases of following the tracks of desulfurizer A; When find the conventional catalyst of desulfurizer A can not meet purification require time, A groove is excised, only uses B groove, change A groove catalyst as early as possible.Under conventional catalyst uses normal situation, when the material sulfur content entering high accuracy desulphurization catalyst of the present invention is lower than 0.5ppm, catalyst of the present invention is used easily the sulphur in material to be taken off 5ppb or following.
Compared with prior art, the present invention has following beneficial effect:
The high-precision catalyst of the present invention, catalyst serviceability temperature is wide, DEG C all can to use from normal temperature ~ 450, working sulfur capacity 250 DEG C time can reach 33%, in DEG C temperature range of normal temperature ~ 450 as feed sulphur content≤0.5ppm, can guarantee that desulfurization is to 5ppb or lower, catalyst long service life, during normal use, the life-span reaches 30 years or more.Save time and the operating cost of user, avoid the accident of the improper damage catalyst of user operation.
Accompanying drawing explanation
The product thermal multigraph of Fig. 1 embodiment 1;
Thing phase during the high accuracy desulphurization catalyst oxidation state of Fig. 2 embodiment 1;
Fig. 3 hydrodesulfurization schematic flow sheet of the present invention;
Fig. 4 hds evaluation device of the present invention;
Wherein: 1-electronic scale; 2-container; 3-pump; 4-hydrogen; 5-heat exchanger; 6-hydrogenation reactor; 7-zinc oxide reactor; 8-fine de-sulfur reactor; 9-condenser; 10-gs-oil separator.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further.
The activity rating method of catalyst:
Catalyst: the former particle of granularity, loading amount 500mL.
Reducing condition: hydrogen+nitrogen is medium, pressure 0.5MPa, bed temperature 220 DEG C, initial hydrogen purity is 1%, improves hydrogen purity to 100% gradually, controls bed temperature rise <20 DEG C.
Operating condition: oil product liquid air speed 2.5h
-1, pressure 2.0MPa, hydrogen 2000mL/min, bed temperature normal temperature-450 DEG C.
Embodiment 1
High accuracy desulphurization catalyst is prepared in the following manner:
1366.7gCu (NO
3)
23H
2o, 1644.8gZn (NO
3)
26H
2o, 294.3gAl (NO
3)
39H
2o, 55.1gZr (NO
3)
45H
2o is soluble in water, is mixed with the mixed solution A of 10L.
By 1593.0gNa
2cO
3be mixed with 10L solution B.
Solution A is warmed up to 85 DEG C, solution B is warmed up to 80 DEG C.
Solution B is placed in reactor, turn on agitator, ultrasonic wave, ultrasonic frequency is 50KHz, sound intensity 0.5W/cm
2, mixing speed controls at 0.30rad/s.Be added drop-wise in solution B with 85 minutes by solution A, neutralization precipitation, rate of addition is 125mL/min.
After dropping terminates, be 50KHz in ultrasonic frequency, sound intensity 1W/cm
2under, maintaining stirring 30 minutes, is 9 by the pH value of Accurate pH measurement slurries.
Slurries are static aging 2h under the temperature conditions of 80 DEG C.
Utilize filter washing equipment to wash slurries, use 80 DEG C of deionized water cyclic washings, when filter cake is colourless through washing to 0.1% concentration diphenylamines sulphate reagent titration, thinks and reach washing terminal.
Filter cake is after 120 DEG C of dry 24h, and send into roaster, be heated to 650 DEG C, carry out the dehydration Sum decomposition of 4h, constant temperature 4h, namely obtains semi-finished product.
Get 500g semi-finished product, add 15g graphite, ball milling crossed 120 mesh sieves after 15 minutes.
Get the material after sieving, add 80gH
2o, mixes, and rolls, granulation, crosses 20 mesh sieves.
Get the material after sieving, compressing with forming machine.
Final gained catalyst cylindrical shape, diameter 6mm, height 6mm, bulk density is 0.84g/mL, side pressure breaking strength 308N/cm.
Sample analysis after the full bed of catalyst 450 DEG C carries out test 100h, the results are shown in Table 1:
Table 1 raw material hydrodesulfurization analysis result
| Project | Green oil | After zinc oxide desulfurization | After fine de-sulfur |
| Sulfur content | 10ppm | 0.51ppm | 3ppb |
The particle diameter drawing off sample is measured, shot copper footpath 7.5nm, zinc oxide particle diameter 11nm with X-ray diffraction method.
Measure fresh catalyst pore structure, pore-size is being less than the aperture of 10nm, accounts for 92.1% of total hole volume.
Chemical analysis metal oxidation state ratio is roughly:
CuO：ZnO：Al
2O
3：ZrO
2＝45：45：8：2
The sample of Example 1, working sulfur capacity test is carried out at 250 DEG C, use the oil product of total sulfur 500ppm, the reactor that sample is housed directly is entered after hydrogenation, the hydrogen sulfide content of analysis reactor entrance, outlet, only be not changed to entering, exporting hydrogen sulfide content, analyze the sulfur content measuring and draw off sample, sample penetration Sulfur capacity reaches 33.6%.
Comparative example 1
Catalyst is prepared in the following manner:
1366.7gCu (NO
3)
23H
2o, 1644.8gZn (NO
3)
26H
2o, 294.3gAl (NO
3)
39H
2o is soluble in water, is mixed with the mixed solution A of 10L, solution A is warmed up to 85 DEG C
By 1572.0gNa
2cO
3be mixed with 10L solution B, solution B is warmed up to 80 DEG C.
Solution B is placed in reactor, turn on agitator, ultrasonic wave, ultrasonic frequency is 50KHz, sound intensity 0.5W/cm
2, mixing speed controls at 0.30rad/s.Be added drop-wise in solution B with 85 minutes by solution A, neutralization precipitation, rate of addition is 120mL/min.
After dropping terminates, be 50KHz in ultrasonic frequency, sound intensity 1W/cm
2under, maintaining stirring 15 minutes, is 9 by the pH value of Accurate pH measurement slurries.
Slurries are static aging 2h under the temperature conditions of 80 DEG C.
Utilize filter washing equipment to wash slurries, use 80 DEG C of deionized water cyclic washings, when filter cake is colourless through washing to 0.1% concentration diphenylamines sulphate reagent titration, thinks and reach washing terminal.
Filter cake is after 120 DEG C of dry 24h, and send into roaster, be heated to 600 DEG C, carry out the dehydration Sum decomposition of 4h, constant temperature 4h, namely obtains semi-finished product.
Get 500g semi-finished product, add 15g graphite, ball milling crossed 120 mesh sieves after 15 minutes.
Get the material after sieving, add 80gH
2o, mixes, and rolls, granulation, crosses 20 mesh sieves.
Get the material after sieving, compressing with forming machine.
Final gained catalyst cylindrical shape, diameter 6mm, height 6mm, bulk density is 0.83g/mL, side pressure breaking strength 311N/cm.
Sample analysis after the full bed of catalyst 450 DEG C carries out test 100h, the results are shown in Table 2:
Table 2 raw material hydrodesulfurization analysis result
| Project | Green oil | After zinc oxide desulfurization | After fine de-sulfur |
| Sulfur content | 10ppm | 0.50ppm | 24ppb |
The particle diameter drawing off sample is measured, shot copper footpath 7.6nm, zinc oxide particle diameter 19nm with X-ray diffraction method.
Measure catalyst pore structure, pore-size is being less than the aperture of 10nm, accounts for 91.9% of total hole volume.
Chemical analysis metal oxidation state ratio is:
CuO：ZnO：Al
2O
3＝45：45：8。
Catalyst bulk density 0.80kg/L.
Embodiment 2-3, comparative example 2-3
The preparation method of the high accuracy desulphurization catalyst of the present embodiment is identical with embodiment 1, and difference is, parameter is different, and catalyst composition, character, result of the test are as shown in table 3:
Table 3 catalyst composition, character and result of the test
Comparative example 4
Get industrialized catalyst S T-101, test under similarity condition, recording working sulfur capacity is 18.3%.
Cu-series catalyst is all very strong to the ability that removes of sulphur, and methanol synthesis catalyst is also Cu-series catalyst, and get industrialized catalyst and carry out Experimental Comparison, appreciation condition is identical with embodiment 1, and evaluation result is in table 4.
Table 1 catalyst metals oxidation state ratio
Comparative example 5
CN95103654 describes a kind of CuZnAl catalyst of synthesising gas systeming carbinol, has prepared sample according to embodiment 1, and carry out comparative evaluation with embodiment 1, comparative example 1, appreciation condition, with embodiment 2, the results are shown in Table 5:
Table 5 raw material hydrodesulfurization analysis result
The particle diameter drawing off CN95103654 sample is measured, shot copper footpath 121nm, zinc oxide particle diameter 65nm with X-ray diffraction method.Illustrate that the difference of preparation method has remarkable impact to catalyst performance.
Comparative example 6
CN88108807 describes a kind of preparation method of desulfurizing agent, has prepared sample according to embodiment 4, carries out comparative evaluation, control identical feed space velocity with embodiments of the invention 1, temperature 350 DEG C, and pressure 0.8MPa, the results are shown in Table 6:
Table 6 raw material hydrodesulfurization analysis result
Illustrate that the high-temperature stability of comparative catalyst is slightly poor, affect its clean-up effect.
Claims (10)
1. a high accuracy desulphurization catalyst, is characterized in that, with weight parts, raw material is composed as follows:
Metallic salt, by oxide weight: CuO42-47 part, ZnO42-47 part, Al
2o
35-12 part; ZrO
20.5-5 part; Wherein, the molar ratio of copper zinc is 1:1;
Lubricant 3-5 part;
Precipitating reagent 100-198 part;
Water 5-15 part.
2. high accuracy desulphurization catalyst according to claim 1, is characterized in that, lubricant is any one or a few in graphite, paraffin or stearate; Precipitating reagent be in NaOH or sodium carbonate any one or multiple.
3. the preparation method of a high accuracy desulphurization catalyst according to claim 1, it is characterized in that, by copper, zinc, aluminium, be heated to 45-90 DEG C after the salting liquid of zirconium mixes mutually and obtain solution A, precipitating reagent is mixed with solution, obtain solution B, under 0.20-0.42rad/s mixing speed, solution A is added drop-wise in solution B and carries out precipitation reaction, then carry out aging to material, after aging end, material is washed, dry, mixed material is obtained after roasting kinetics, lubricant is added at mixed material, mix, obtained semi-finished product catalyst, add water in semi-finished product catalyst, compressing.
4. the preparation method of high accuracy desulphurization catalyst according to claim 3, is characterized in that, the metal ion molar concentration of copper, zinc, aluminium, zirconium mixed aqueous solution is 1.0-4.0mol/L; The metal ion molar concentration of the precipitating reagent aqueous solution is 0.5-3.0mol/L.
5. the preparation method of high accuracy desulphurization catalyst according to claim 3, is characterized in that, the solution temperature of solution A is than solution B solution temperature height 2-5 DEG C.
6. the preparation method of high accuracy desulphurization catalyst according to claim 3, is characterized in that, the speed that solution A is added drop-wise to solution B is 0.1-0.4mol/min.
7. the preparation method of high accuracy desulphurization catalyst according to claim 3, is characterized in that, ultrasonic frequency is 45 ~ 50KHz, and the sound intensity is generally 0.5 ~ 1.5W/cm
2.
8. the preparation method of high accuracy desulphurization catalyst according to claim 3, it is characterized in that, precipitation reaction terminates, and slurry pH value is 8.5-9.
9. the preparation method of high accuracy desulphurization catalyst according to claim 3, is characterized in that, aging temperature is 45-90 DEG C, and ageing time is 1-12 hour.
10. the preparation method of high accuracy desulphurization catalyst according to claim 3, is characterized in that, sediment sintering temperature is 600-650 DEG C, and roasting time is 1-6h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109012678A (en) * | 2018-08-27 | 2018-12-18 | 鲁西催化剂有限公司 | A kind of high dispersive desulphurization catalyst preparation method |
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| CN1151333A (en) * | 1995-06-07 | 1997-06-11 | 菲利浦石油公司 | Sorbent compositions |
| US20030162659A1 (en) * | 2002-02-28 | 2003-08-28 | Slimane Rachid B. | ZnO-based regenerable sulfur sorbents for fluid-bed/transport reactor applications |
| CN103525474A (en) * | 2013-10-30 | 2014-01-22 | 西南化工研究设计院有限公司 | Ultrafine desulfurization agent and preparation method thereof |
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2014
- 2014-10-09 CN CN201410527456.3A patent/CN105562006A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1151333A (en) * | 1995-06-07 | 1997-06-11 | 菲利浦石油公司 | Sorbent compositions |
| US20030162659A1 (en) * | 2002-02-28 | 2003-08-28 | Slimane Rachid B. | ZnO-based regenerable sulfur sorbents for fluid-bed/transport reactor applications |
| CN103525474A (en) * | 2013-10-30 | 2014-01-22 | 西南化工研究设计院有限公司 | Ultrafine desulfurization agent and preparation method thereof |
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| CN109012678A (en) * | 2018-08-27 | 2018-12-18 | 鲁西催化剂有限公司 | A kind of high dispersive desulphurization catalyst preparation method |
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