CN105727960A - A preparing method of a methanol synthesis catalyst used for a slurry bed - Google Patents
A preparing method of a methanol synthesis catalyst used for a slurry bed Download PDFInfo
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- CN105727960A CN105727960A CN201410757997.5A CN201410757997A CN105727960A CN 105727960 A CN105727960 A CN 105727960A CN 201410757997 A CN201410757997 A CN 201410757997A CN 105727960 A CN105727960 A CN 105727960A
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Abstract
The invention relates to a preparing method of a methanol synthesis catalyst used for a slurry bed, and belongs to the field of catalyst preparation. The method is characterized in that one or more alkalis are adopted as a precipitant and are subjected to stream combination with a copper zinc mixed solution; before stream combination, deionized water is added into a stream combining barrel, treated crystal seeds are dissolved in the water, the water is heated to 60-100 DEG C and subjected to stream combination, a prepared catalyst precursor and mother liquor are boiled, filtered and washed, conductivity of a solution at a washing end point is controlled to be not more than 10 [mu]s/cm, the catalyst precursor is prepared into slurry, the slurry is granulated and dried through spray drying, spray-dried particles are calcinated at 300-400 DEG C for 30-120 min, a proper amount of a lubricant is added into the calcinated particles, the obtained mixture is tabletted and molded with the strength of tablets is controlled, the molded catalyst tablets are smashed into particles, and an adhesive and water are added into the smashed particles and subjected to secondary molding to prepare the methanol synthesis catalyst. The catalyst is suitable for methanol preparation from synthetic gas containing CO, CO2 and H2, and is particularly suitable for a slurry bed methanol synthesis device.
Description
Technical field
The invention belongs to catalyst preparation technical field, be specifically related to a kind of methanol synthesis catalyst preparation method used for slurry bed.
Background technology
The methyl alcohol synthetic reactor of current industrial employing is vapor solid fixed bed reaction tower, and shortcoming is that reaction temperature control is more difficult, and temperature runaway easily occurs in bed.Owing to methanol-fueled CLC reaction is strong exothermal reaction, Cu-series catalyst heat stability used is poor, if reaction temperature is best interval beyond it, will cause that catalyst inactivates because of thermal sintering.In order to keep the reaction bed temperature rise tolerance range without departing from Cu-series catalyst, synthesis gas conversion per pass must control in relatively low scope (general 10%-15%), causes the higher (H of hydrogen-carbon ratio of reaction gas by synthetic tower2/ CO=(5-10): 1), gas circulates relatively larger (more than 5), and the methanol concentration ultimately resulting in synthetic tower outlet is not too high (3%-6%).
Compared with vapor solid fixed bed reaction system, airwater mist cooling slurry bed system feature at the paraffin class long-chain hydrocarbon compound big with employing thermal capacitance height, heat conductivity as liquid phase medium, again due to violent disturbance so that bed temperature is uniformly easily-controllable.This allows for airwater mist cooling methanol-fueled CLC response system can adopt the unstripped gas of high CO concentration, improves CO and H in unstripped gas2Conversion ratio, use armatine determining alcohol and may be up to 15%-20%, and bed does not still have hot-spot and the excessive situation of temperature rise.
In general, the catalyst used by airwater mist cooling methanol synthesis in slurry reactor technique is essentially all the business CuO/ZnO/Al for vapor solid fixed-bed process2O3Catalyst.U.S. AirProductsandChemicals once in depth tested some commercial catalysts, and (code name is 35,38,40,42 and 43, the model that non-catalytic manufacturer specifies), and the character of S3-85 and S3-86 catalyst that produces of Germany BASF and be used in the performance in slurry bed system methanol synthesizing process.Wherein, code name is that the catalyst of 43 has minimum slurry viscosity (slurryviscosity) and the highest loading capacity (packedvolume) in solvent naphtha, is proposed as the optimal catalyst for methanol synthesis in slurry reactor technique.The BET specific surface area of this catalyst is 87.4m2/ g, specific pore volume is 0.588m3/g.U.S.'s AkronUniversity and BertyReactionEngineers, Ltd. research worker thinks that the catalyst that code name is EPJ-19 that UitedCatalyst, Inc. produce can be used in methanol synthesis in slurry reactor technique.The BET specific surface area of this catalyst is 80-92m2/ g, specific pore volume is 0.43m3/ g, average pore size is 20nm, and after reduction, in untapped catalyst, the average diameter of metallic copper crystallite is 3.77nm.It addition, Graaf etc. have studied catalyst HaldorTopsoeMK101 kinetics in methanol synthesis in slurry reactor；Ledakowicz etc. have studied the Germany BASF catalyst S3-85 produced and Poland NitrogenWorks catalyst BT-d produced performance in methanol synthesis in slurry reactor technique；Fang Dingye and Zhu Ping Chen etc. have studied catalyst C302 performance in methanol synthesis in slurry reactor technique.The Institutes Of Technology Of Taiyuan Zhang little Bing evaluation by slurry bed system system for methanol synthesis, prepares CuO/ZnO/Al to coprecipitation2O3Catalyst is optimized, and result shows at 240 DEG C, 4.0MPa, H2/CO/CO2=92/36/7 and air speed be under 810ml/gcat h, through optimization to reaction condition, the space-time yield of methanol and the inactivation rate of catalyst have respectively reached 166.7g/kgcat h and 0.16%/d.Inactivation rate is lower than the minimum 0.18%/d of bibliographical information, and namely U.S.'s air products and chemical company carry out the minimum of used catalyst inactivation rate during methanol synthesis in slurry reactor industrial test.
A few studies personnel have carried out the research that special preparation is suitable for the catalyst of methanol synthesis in slurry reactor technique.Itoh etc. are by reducing agent (NaBH4, KBH4Or LiAlH4Aqueous solution) join in the solution containing copper and zinc salt (Cu/Zn=7/3, mol ratio), precipitate water and washing with acetone, then dry in vacuum again, prepared and there is highly active methanol synthesis catalyst in slurry bed system.Zhu Ping Chen etc. are prepared for the Cu/ZnO/Al for methanol synthesis in slurry reactor technique by coprecipitation2O3Catalyst, called after TPM-1.This catalyst is in use for laboratory mechanical agitation slurry reactor still, with CO11%, CO216% and H2The unstripped gas of 69%, reaction condition be 5.0MPa, 250 DEG C time, reactor outlet methanol content more than 7%, and carried out 240h life-span investigate experiment.
The preparation method that Chinese patent CN200780005726.2 discloses a kind of slurry bed system methanol synthesis catalyst.This catalyst will containing alkali metal formate load on Cu/MgO solid catalyst, can simultaneously one or both in load Na, Pd.
The preparation method that Chinese patent CN201110064737.6 discloses a kind of slurry bed system methanol synthesis catalyst.This catalyst is made up of copper zinc (can containing aluminum zirconium) active component presoma and binding agent.
The preparation method that Chinese patent CN201080026702.7 discloses a kind of slurry bed system methanol synthesis catalyst.This catalyst is made up of the oxide of one or more in copper zinc-aluminium and further auxiliary, and auxiliary agent has Mg, Cr, Mn, V, Ti, Zr, Ta, Mo, W, Si.
Summary of the invention
The purpose of the present invention is to propose to a kind of methanol synthesis catalyst preparation method used for slurry bed.
The methanol synthesis catalyst effective active component Cu/Zn mol ratio used for slurry bed being mainly characterized by preparing by this method of the present invention is high, has higher intensity, methanol selectivity and combination property.
Methanol synthesis catalyst preparation method used for slurry bed of the present invention, is characterized in that adopting one or more alkali as precipitant and copper zinc mixed liquor and to flow；And before flowing, and flow in bucket addition deionized water, water is dissolved with the crystal seed processed, then heats the water to 60～100 DEG C, and flow；The catalyst precursor obtained and mother solution heat are boiled, filters, wash, the electrical conductivity≤10 μ s/cm of washing terminal point control solution；Catalyst precursor being made slip, carries out pelletize and dry by spray drying, spray dried particle through calcining 30～120min under 300 ~ 400 DEG C of conditions；Lubricant is added after above-mentioned calcining in particle, carry out playing sheet molding, control tablet strength；Catalyst tablet after molding is broken into particle, adds binding agent and methanol synthesis catalyst is made in water, post forming.
Normally, described precipitant alkali is sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate or sodium hydroxide.
In described copper zinc two component methanol synthesis catalyst, copper zinc atom mol ratio interval is 2.0 ~ 3.5.
The presoma that crystal seed is finished catalyst effective active component added before described preparation.
The amount of the crystal seed added before described preparation is and flows 0.5%～5% by the copper and zinc deposit gross mass contained in copper zinc mixed liquor.
Described presoma and mother solution heat under 60～100 DEG C of conditions boils 30～120min.
Presoma after described washing makes slip before spraying, and slurry solid content is 10%～40%(mass content).
Described first time plays sheet molding, controls tablet strength at 150～250N/cm, and the catalyst tablet after molding is broken into the particle of 20～250 orders, and second time molding time control tablet strength is at 200～350N/cm.
Add 0.5% ~ 10%(mass content during described second time molding) binding agent and 0.5%～3%(mass content) water be shaping assistant.
Described binding agent is one or more in sesbania powder, kieselguhr and cellulose.
The invention have the advantage that the methanol synthesis catalyst used for slurry bed prepared according to this method has higher selectivity, bigger intensity and longer life-span.
Detailed description of the invention
Examples below is in order to further illustrate present disclosure:
Example 1
Sodium bicarbonate is adopted to obtain catalyst precursor as precipitant, copper zinc atom ratio 2.0, spray drying granulation, spray particle calcines 120min through calcining furnace at 300 DEG C, first molding, adds 10% sesbania powder after broken, methanol synthesis catalyst cat1 is made in post forming.
Example 2
Sodium carbonate is adopted to obtain catalyst precursor as precipitant, copper zinc atom ratio 2.5, spray drying granulation, spray particle calcines 60min through calcining furnace at 350 DEG C, first molding, adds 5% kieselguhr after broken, methanol synthesis catalyst cat2 is made in post forming.
Example 3
Potassium carbonate is adopted to obtain catalyst precursor as precipitant, copper zinc atom ratio 3.0, spray drying granulation, spray particle calcines 30min through calcining furnace at 400 DEG C, first molding, adds 0.5% cellulose after broken, methanol synthesis catalyst cat3 is made in post forming.
Example 4
Potassium bicarbonate is adopted to obtain catalyst precursor as precipitant, copper zinc atom ratio 3.5, spray drying granulation, spray particle calcines 90min through calcining furnace at 330 DEG C, first molding, adds 2% sesbania powder after broken and methanol synthesis catalyst cat4 is made in 2% cellulose, post forming.
Contrast sample
Adopt Cu catalyst based ternary parent (the copper zinc atom ratio 2.8, Al that sodium bicarbonate obtains as the precipitant of parent2O3Mass content 9%) carry out pelletize by spray drying, carry out pelletize by spray drying, spray dried particle enter calcining furnace 350 DEG C carries out calcining 40min, then economy-combat sheet molding procedure prepares this catalst for synthesis of methanol cat0.
Sample test
Catalyst sample: granularity is 0.425～1.180mm.
Activity determination: adopting slurry bed system continuous flow reactor, the loadings 10g of catalyst, the reduction of catalyst is at Gao Qing (H2∶N2=95: 5), in atmosphere, temperature programming (40 DEG C/h) is reduced about 5 hours, and temperature rises to 230 DEG C.Reducing gases is switched to unstripped gas and carries out active testing.Active testing condition is reaction pressure 5.0MP, air speed 10000h-1, temperature 230 DEG C, synthesis gas forms: H2∶CO∶CO2∶N2, activity value to generate the space-time yield (gml of methanol=65: 14: 4: 17(v/v)-1h-1) represent.Adopting Agilent 7890 gas chromatogram that the methanol gas in tail gas is analyzed, activity and intensity results are in shown in table 1.Wherein sample cat1, cat2, cat3 is prepared by preparation method of the present invention, and sample cat0 is reference.
Table 1 methanol selectivity test result
| Catalyst | cat1 | cat2 | cat3 | cat0 |
| Selectivity/% | 18.5 | 21.3 | 19.0 | 4.76 |
Table 2 catalyst effective active component Cu/Zn mol ratio
| Catalyst | cat1 | cat2 | cat3 | cat0 |
| Surface | 3.16 | 3.02 | 2.78 | 2.28 |
Strength test results after the use of table 3 catalyst
| Catalyst | cat1 | cat2 | cat3 | cat0 |
| Use rear intensity/N/cm | 151 | 144 | 155 | 70 |
Being can be seen that by table 1, table 2 and table 3, adopting methanol synthesis catalyst prepared by the inventive method to compare with reference, effective active component Cu/Zn mole is high, causes that the effective rate of utilization of activity Cu is improved so that methanol selectivity is significantly raised；It can be seen that catalyst prepared by the inventive method also has higher mechanical strength the intensity after use, thus ensure that catalyst has good mechanical stability in slurry reactor.
Claims (10)
1. a methanol synthesis catalyst preparation method used for slurry bed, is characterized in that adopting one or more alkali as precipitant and copper zinc mixed liquor and to flow；And before flowing, and flow in bucket addition deionized water, water is dissolved with the crystal seed processed, then heats the water to 60～100 DEG C, and flow；The catalyst precursor obtained and mother solution heat are boiled, filters, wash, the electrical conductivity≤10 μ s/cm of washing terminal point control solution；Catalyst precursor being made slip, carries out pelletize and dry by spray drying, spray dried particle through calcining 30～120min under 300 ~ 400 DEG C of conditions；Lubricant is added after above-mentioned calcining in particle, carry out playing sheet molding, control tablet strength；Catalyst tablet after molding is broken into particle, adds binding agent and methanol synthesis catalyst is made in water, post forming.
2. methanol synthesis catalyst preparation method used for slurry bed according to claim 1, it is characterised in that described precipitant alkali is sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate or sodium hydroxide.
3. methanol synthesis catalyst preparation method used for slurry bed according to claim 1, it is characterised in that in copper zinc two component methanol synthesis catalyst, copper zinc atom molar ratio interval is 2.0 ~ 3.5.
4. methanol synthesis catalyst preparation method used for slurry bed according to claim 1, it is characterised in that the presoma that crystal seed is finished catalyst effective active component added before preparation.
5. methanol synthesis catalyst preparation method used for slurry bed according to claim 1 or 4, it is characterised in that the amount of the crystal seed added before preparation is and flows 0.5%～5% by the copper and zinc deposit gross mass contained in copper zinc mixed liquor.
6. methanol synthesis catalyst preparation method used for slurry bed according to claim 1, it is characterised in that presoma and mother solution heat under 60～100 DEG C of conditions boils 30～120min.
7. methanol synthesis catalyst preparation method used for slurry bed according to claim 1, it is characterised in that the presoma after washing makes slip before spraying, and slurry solid content mass content is 10%～40%.
8. methanol synthesis catalyst preparation method used for slurry bed according to claim 1, it is characterized in that first time plays sheet molding, control tablet strength at 150～250N/cm, catalyst tablet after molding is broken into the particle of 20～250 orders, and second time molding time control tablet strength is at 200～350N/cm.
9. methanol synthesis catalyst preparation method used for slurry bed according to claim 1, the water adding mass content 0.5% ~ 10% binding agent and mass content 0.5%～3% when it is characterized in that second time molding is shaping assistant.
10. methanol synthesis catalyst used for slurry bed and preparation method thereof according to claim 1 or 9, it is characterised in that described binding agent is one or more in sesbania powder, kieselguhr and cellulose.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110898840A (en) * | 2018-09-18 | 2020-03-24 | 中国石油化工股份有限公司 | Methanol synthesis catalyst and preparation method thereof |
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| CN110898840A (en) * | 2018-09-18 | 2020-03-24 | 中国石油化工股份有限公司 | Methanol synthesis catalyst and preparation method thereof |
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