CN102179251B - Catalyst for synthesizing methanol by fluidized bed and preparation method thereof - Google Patents
Catalyst for synthesizing methanol by fluidized bed and preparation method thereof Download PDFInfo
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- CN102179251B CN102179251B CN2011100647376A CN201110064737A CN102179251B CN 102179251 B CN102179251 B CN 102179251B CN 2011100647376 A CN2011100647376 A CN 2011100647376A CN 201110064737 A CN201110064737 A CN 201110064737A CN 102179251 B CN102179251 B CN 102179251B
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011230 binding agent Substances 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 29
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical group [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 14
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- 230000001376 precipitating effect Effects 0.000 claims description 11
- 238000001694 spray drying Methods 0.000 claims description 11
- 229910052725 zinc Inorganic materials 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 229940072033 potash Drugs 0.000 claims description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 7
- 235000015320 potassium carbonate Nutrition 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 5
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 5
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- BNUDRLITYNMTPD-UHFFFAOYSA-N acetic acid;zirconium Chemical compound [Zr].CC(O)=O BNUDRLITYNMTPD-UHFFFAOYSA-N 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 3
- 229940009827 aluminum acetate Drugs 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 15
- 229910052802 copper Inorganic materials 0.000 abstract description 9
- 239000010949 copper Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- 239000012530 fluid Substances 0.000 description 14
- 238000001556 precipitation Methods 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000008187 granular material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910017773 Cu-Zn-Al Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- -1 high stability Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a catalyst for synthesizing methanol by a fluidized bed and a preparation method thereof. The catalyst is obtained by calcining a mixture of an active component precursor and a binding agent. According to the weight percentage of oxides, the mixture contains the following materials: 30wt%-80wt% of active component precursor and 20wt%-70wt% of binding agent, wherein the binding agent is zirconium gel. According to the catalyst for synthesizing methanol by the fluidized bed disclosed by the invention, as the zirconium gel is adopted as the binding agent, the catalyst synthesized by copper-based methanol can have enough mechanical strength and wear resistance under the premise that high activity and high stability of the catalyst synthesized by the copper-based methanol are kept, so that the catalyst can be used as a catalyst for synthesizing the methanol by a fluidized bed reactor.
Description
Technical field
The present invention relates to catalyst preparation technical field, particularly, relate to the synthesizing methanol by fluidized bed Catalysts and its preparation method.
Background technology
Since the invention Cu-Zn-Al of the ICI company catalyst for synthesizing copper based methanol of the seventies Britain in last century, the synthesizing methanol technology of filling this catalyst in fixed bed reactors has just occupied leading position in methanol industry.Yet, because co hydrogenation and hydrogenation of carbon dioxide that the methyl alcohol synthetic reaction relates to all are strong exothermal reactions, and catalyst for synthesizing copper based methanol will sintering deactivation under higher temperature, therefore, for large-scale fixed bed industrial reaction device, it is relatively more difficult moving timely and effectively heat and controlling reactor various piece temperature stable homogeneous.At present, industrial employing calandria type fixed bed reactor, not only equipment is processed, the maintenance difficulty is larger.In addition, in order to control the temperature rise of reaction, the conversion rate control of having to react is in lower scope, thereby so that a large amount of unconverted reaction raw materials gas needs to reclaim, circulation, this not only causes the utilization rate of equipment low, and operation energy consumption is large.
Fluidized-bed reactor has the advantages such as heat-transfer effect is good, uniformity of temperature profile, and the catalyst inside diffusional resistance is little, but the collision friction of catalyst and reactor wall is violent, and is high to mechanical strength and the wearability requirement of catalyst granules.
For mechanical strength and the wearability that improves catalyst, proposed active component is mixed with binding agent the spherical granule that obtains by the mist projection granulating moulding.Binding agent uses the clays such as Ludox, aluminium colloidal sol and kaolin usually.Therefore yet existing catalyst namely loses activity usually in a short period of time, causes the life cycle of catalyst shorter, production cost improves.
Summary of the invention
The present invention is intended to solve at least one of above-mentioned technological deficiency.
For this reason, the purpose of a first aspect of the present invention is to propose a kind of fluid bed methanol synthesis catalyst, it can possess enough mechanical strengths and mar proof when keeping catalyst for synthesizing copper based methanol high activity, high stability, satisfy the instructions for use of fluid bed.
The purpose of a second aspect of the present invention is to propose a kind of preparation method of fluid bed methanol synthesis catalyst.
In order to achieve the above object, fluid bed methanol synthesis catalyst according to first aspect present invention embodiment, mixture by active component presoma and binding agent obtained 150～400 degrees centigrade of lower spray-dryings and 300～450 degrees centigrade of lower calcinings in 1～3 hour, it is characterized in that, with the weight percent meter of oxide, contain in the described mixture: the active component presoma of 30wt%～80wt%; And the binding agent of 20wt%～70wt%, wherein, described binding agent is the zirconium gel, in the molar fraction of metallic atom, contains in the described active component presoma: the copper atom of 30～80 molar fractions; The zinc atom of 20～40 molar fractions; The aluminium atom of 0～15 molar fraction; Zirconium atom with 0～15 molar fraction.
Fluid bed methanol synthesis catalyst according to the embodiment of the invention, owing to adopting the zirconium gel as described binding agent, can be under the prerequisite that keeps catalyst for synthesizing copper based methanol high activity, high stability, make catalyst for synthesizing copper based methanol possess enough mechanical strengths and mar proof, thereby can be used as the methanol synthesis catalyst of fluidized-bed reactor.
In addition, the fluid bed methanol synthesis catalyst according to the embodiment of the invention can also have following additional technical feature:
According to some embodiments of the present invention, described zirconium gel is zirconium hydroxide gel or zirconyl hydroxide gel.
According to some embodiments of the present invention, described synthesizing methanol by fluidized bed is 0.6～1.0g/ml with the size distribution of catalyst at 20～300 μ m and bulk density.
Preparation method according to the fluid bed methanol synthesis catalyst of second aspect present invention embodiment may further comprise the steps:
A) make soluble metallic salt and carbonate or bicarbonate under condition of heating and stirring, coprecipitation reaction occur, obtain the active component presoma, contain soluble copper salt, soluble zinc salt, aluminum soluble salt and solubility zirconates in the described soluble metallic salt;
B) zirconates and precipitating reagent are reacted under condition of heating and stirring, reaction is stirred and is left standstill after finishing, and obtains the zirconium gel;
C) described active component presoma is mixed with described zirconium gel, obtain mixture; With
D) with described mixture 150～400 degrees centigrade of lower spray-dryings, and 300～450 degrees centigrade of lower calcinings 1～3 hour, obtain described synthesizing methanol by fluidized bed catalyst,
Wherein, with the weight percent meter of oxide, contain the described active component presoma of 30wt%～80wt% and the described zirconium gel of 20wt%～70wt% in the described mixture,
In the molar fraction of metallic atom, contain in the described active component presoma: the copper atom of 30～80 molar fractions; The zinc atom of 20～40 molar fractions; The aluminium atom of 0～15 molar fraction; Zirconium atom with 0～15 molar fraction.
Preparation method according to the fluid bed methanol synthesis catalyst of the embodiment of the invention, owing to adopting the zirconium gel as described binding agent, can be under the prerequisite that keeps catalyst for synthesizing copper based methanol high activity, high stability, make catalyst for synthesizing copper based methanol possess enough mechanical strengths and mar proof, thereby preparation is applicable to the methanol synthesis catalyst of fluidized-bed reactor.
In addition, the preparation method according to the fluid bed methanol synthesis catalyst of the embodiment of the invention can also have following additional technical feature:
According to some embodiments of the present invention, described soluble copper salt comprises copper nitrate, Schweinfurt green or its combination, described soluble zinc salt comprises zinc nitrate, zinc acetate or its combination, described aluminum soluble salt comprises aluminum nitrate, aluminum acetate or its combination, and described solubility zirconates comprises zirconium nitrate, acetic acid zirconium or its combination.
According to some embodiments of the present invention, step a) in, described carbonate is sodium carbonate or potash, described bicarbonate is sodium acid carbonate or saleratus.
According to some embodiments of the present invention, step b) in, described zirconates is one or more in zirconyl nitrate, zirconium oxychloride, the zirconium nitrate, and described precipitating reagent is one or more in NaOH, potassium hydroxide, sodium carbonate, potash, sodium acid carbonate or the saleratus.
Additional aspect of the present invention and advantage in the following description part provide, and part will become obviously from the following description, or recognize by practice of the present invention.
The specific embodiment
The below describes embodiments of the invention in detail, and the following examples are exemplary, only is used for explaining the present invention, and can not be interpreted as limitation of the present invention.
Preparation method according to the fluid bed methanol synthesis catalyst of the embodiment of the invention is at first described.
A) preparation active component presoma
Make soluble metallic salt and carbonate or bicarbonate under condition of heating and stirring, coprecipitation reaction occur, obtain the active component presoma.
Wherein, described carbonate is sodium carbonate or potash, and described bicarbonate is sodium acid carbonate or saleratus.
Contain soluble copper salt, soluble zinc salt, aluminum soluble salt and solubility zirconates in the described soluble metallic salt, wherein, the molar fraction in metallic atom contains: the copper atom of 30～80 molar fractions, the zinc atom of 20～40 molar fractions, the aluminium atom of 0～15 molar fraction, and the zirconium atom of 0～15 molar fraction, preferably, contain: the copper atom of 60 molar fractions, the zinc atom of 30 molar fractions, the aluminium atom of 0～10 molar fraction, and the zirconium atom of 0～10 molar fraction.
Described soluble copper salt comprises copper nitrate, Schweinfurt green or its combination, described soluble zinc salt comprises zinc nitrate, zinc acetate or its combination, described aluminum soluble salt comprises aluminum nitrate, aluminum acetate or its combination, and described solubility zirconates comprises zirconium nitrate, acetic acid zirconium or its combination.
Reaction temperature and the reaction time of described coprecipitation reaction do not have particular restriction, for example can carry out under 60～80 degrees centigrade, preferably carry out under 70 degrees centigrade; Reaction time can be 50～70min, is preferably 60min.The result of above-mentioned reaction obtains the active component presoma.
Alternatively, after finishing, reaction can continue to stir precipitation gained slurries to allow aging a period of time of precipitation slurries.After this, can be with dope filtration, with deionized water cyclic washing repeatedly, to remove the foreign ion in the filter cake.
B) preparation zirconium gel
Zirconates and precipitating reagent are reacted under condition of heating and stirring, and reaction is stirred and is left standstill after finishing, and obtains the zirconium gel.
Wherein, described zirconates can be in zirconyl nitrate, zirconium oxychloride, the zirconium nitrate one or more, is preferably zirconyl nitrate.
Described precipitating reagent can be in NaOH, potassium hydroxide, sodium carbonate, potash, sodium acid carbonate or the saleratus one or more, is preferably sodium carbonate.
Reaction temperature and the reaction time of described precipitation reaction do not have particular restriction, and described zirconates and described precipitating reagent are reacted under 60～80 degrees centigrade, preferably 70 degrees centigrade of lower reactions; Reaction time can be 50～70min, is preferably 60min.The result of above-mentioned reaction obtains the agent of zirconium gel cementing
Alternatively, after reaction finishes, continue to stir precipitation gained slurries, allow aging a period of time of precipitation slurries.With dope filtration, with deionized water cyclic washing repeatedly, to remove the foreign ion in the filter cake.
C) described active component presoma is mixed with the agent of described zirconium gel cementing, obtain mixture
Wherein, with the weight percent meter of oxide, contain the described active component presoma of 30wt%～80wt% and the described zirconium gel of 20wt%～70wt% in the described mixture.
D) will calcine after the described mixture spray-drying, obtain described synthesizing methanol by fluidized bed catalyst.
Described mixture 150～400 degrees centigrade of lower spray-dryings, and 300～450 degrees centigrade of lower calcinings 1～3 hour, is obtained described synthesizing methanol by fluidized bed catalyst.
During spray-drying, the slurry fluidity that solid content is low is better, carry and spray-drying than being easier to, but because water content is very high, dry energy consumption is higher.The slurries that solid content is higher, general viscosity is larger, and conveying and spray-drying are not too convenient, but dry energy consumption is lower.The solid content of general slurries can be 10～40%.Spray-dired inlet temperature is generally 150～400 ℃.
Spray-drying obtains the catalyst granules of almost spherical, and then calcining obtains preformed catalyst in Muffle furnace.The temperature of calcining is generally 300～450 ℃.The size distribution of preformed catalyst is at 20～300 μ m, and bulk density is 0.6～1.0g/mL.This catalyst granules belongs to the category-A particle, very easily good fluidisation in fluid bed.
Through above-mentioned steps, obtain after calcining, obtaining the synthesizing methanol by fluidized bed catalyst by the mixture of active component presoma and binding agent, wherein, with the weight percent meter of oxide, contain in the described mixture: the active component presoma of 30wt%～80wt%; And the binding agent of 20wt%～70wt%, wherein, described binding agent is the zirconium gel.Contain cupric oxide, zinc oxide, aluminium oxide and zirconia in the described active component, wherein, in the molar fraction of metallic atom, the copper atom that contains 30～80 molar fractions, the zinc atom of 20～40 molar fractions, the aluminium atom of 0～15 molar fraction, and the zirconium atom of 0～15 molar fraction.
Embodiment 1
In the molar fraction of metallic atom, by the copper atom of 80 molar fractions and the zinc atom of 20 molar fractions copper nitrate and zinc nitrate are added the mixed salt solution that is made into 1.2mol/L in the deionized water.Then the sodium carbonate of stoichiometric number is added in the deionized water and be made into the solution of 1.2mol/L, and be heated to 70 ℃, keep that this is temperature-resistant, slowly splashing into above-mentioned mixed salt solution to the pH value of reacting the gained mixed serum under the rapid stirring is 7.70 ℃ of maintenance systems are constant, continue behind the stirring 60min slurries to be taken out filtration, are lower than 5mg/g with deionized water cyclic washing to concentration impurity ion, obtain the active component presoma of catalyst.
Zirconium oxychloride is added the solution that is made into 0.6mol/L in the deionized water, slowly splashes in the sodium carbonate liquor that is heated to 70 ℃, rapid stirring react to slurry pH value be 7.Stop to splash into zirconium oxychloride aqueous solution, keep 70 ℃, take out behind the rapid stirring 60min, filter, wash to concentration impurity ion with deionized water and be lower than 5mg/g, obtain the zirconyl hydroxide gel.
Active component presoma and the agent of zirconium gel cementing are mixed to get mixture, and 300 degrees centigrade of lower spray-dryings, 400 degrees centigrade of lower calcining 120min obtain the catalyst granules of moulding with mixture.
(that is: active component is respectively with cupric oxide, zinc oxide, aluminium oxide and zirconic weighing scale with the weight percent meter of oxide, the zirconium gel with zirconic weighing scale), contain 70% active component presoma and 30% zirconium gel cementing agent in the described mixture.
Embodiment 2
The present embodiment is basically identical with embodiment 1, difference is: the used slaine of the preparation of catalyst activity component presoma is copper nitrate, zinc nitrate and aluminum nitrate, wherein, in the molar fraction of metallic atom, contain the copper atom of 60 molar fractions, the zinc atom of 30 molar fractions and the aluminium atom of 10 molar fractions; The used precipitating reagent of active component presoma precipitation is sodium acid carbonate; The used precipitating reagent of zirconium gel cementing agent precipitation is NaOH.
Embodiment 3
The present embodiment is basically identical with embodiment 1, difference is: the used slaine of the preparation of catalyst activity component presoma is Schweinfurt green, zinc acetate and acetic acid zirconium, wherein, in the molar fraction of metallic atom, contain the copper atom of 60 molar fractions, the zinc atom of 30 molar fractions and the zirconium atom of 10 molar fractions; The used precipitating reagent of active component presoma precipitation is potash; The used precipitating reagent of zirconium gel cementing agent precipitation is saleratus.
Embodiment 4
The present embodiment is basically identical with embodiment 1, difference is: the used slaine of the preparation of catalyst activity component presoma is copper nitrate, zinc nitrate, aluminum nitrate and zirconium nitrate, wherein, in the molar fraction of metallic atom, contain the copper atom of 60 molar fractions, the zinc atom of 30 molar fractions, the aluminium atom of 5 molar fractions and the zirconium atom of 5 molar fractions; The agent of zirconium gel cementing is prepared by zirconyl nitrate.
Embodiment 5
The present embodiment is basically identical with embodiment 4, and difference is: with the weight percent meter of oxide, contain 80% active component presoma and 20% zirconium gel cementing agent in the described mixture.
Experimental example
Activity and the stability of the catalyst of above embodiment preparation are tested in the miniature fixed-bed reactor in laboratory.Reaction condition is: temperature is 230 ℃, and pressure is 4Mpa, and air speed is 5000mlgcat
-1H
-1React the CO that consists of 26.3vol%, the CO of 5.3vol% of used synthesis gas
2H with 68.4vol%
2Before the reaction, catalyst is at nitrogen and hydrogen mixture (4vol%H
2) middle reduction 10h.
The activity of methanol synthesis catalyst characterizes by the conversion ratio of carbon monoxide and the productive rate of methyl alcohol.Test result is as shown in table 1.As can be seen from Table 1, catalyst according to the invention all has higher activity.
The stability of the catalyst of assessment preparation as an example of embodiment 4 example.Be 260 ℃ in temperature, pressure is 4Mpa, and air speed is 5000mlgcat
-1H
-1Lower, successive reaction 120h gets a sample every a period of time, and to investigate over time situation of the activity of catalyst in course of reaction, its result is as shown in table 2.As can be seen from Table 2, under 260 ℃ of higher reaction temperatures (typical temperature is higher, and catalyst stability is poorer), the activity of reaction 120h rear catalyst does not significantly descend, and can think the good stability of this catalyst.
Based on international ASTM-D-5757-00 standard, abrasion resistance properties by air jet method detecting catalyst, adopt air jet index (its expression catalyst is taken out of the percentage by weight of fluid bed in the wearing and tearing of 5h internal cause for Air Jet Index, AJI) to estimate.Experimental result is as shown in table 1.As can be seen from Table 1, the catalyst according to the above embodiment of the present invention preparation all has good mar proof.
Table 1
| The carbon monoxide conversion ratio | The productive rate of methyl alcohol | Abrasion strength resistance | |
| Embodiment 1 | 0.2234 | 0.4351 | 0.05 |
| Embodiment 2 | 0.3746 | 0.6765 | 0.055 |
| Embodiment 3 | 0.3708 | 0.6696 | 0.051 |
| Embodiment 4 | 0.4207 | 0.8098 | 0.053 |
| Embodiment 5 | 0.2562 | 0.4983 | 0.065 |
Table 2
Fluid bed methanol synthesis catalyst according to the embodiment of the invention, owing to adopting the zirconium gel as binding agent, not only can keep high activity of catalyst, high stability, and catalyst possess enough mechanical strengths and mar proof, the very suitable fluid bed methanol synthesis catalyst that is used as.
In the description of this specification, the description of reference term " embodiment ", " some embodiment " or " example " etc. means to be contained at least one embodiment of the present invention or the example in conjunction with specific features, structure, material or the characteristics of this embodiment or example description.In this manual, the schematic statement of above-mentioned term not necessarily referred to identical embodiment or example.And the specific features of description, structure, material or characteristics can be with suitable mode combinations in any one or more embodiment or example.
Although illustrated and described embodiments of the invention, those having ordinary skill in the art will appreciate that: in the situation that do not break away from principle of the present invention and aim can be carried out multiple variation, modification, replacement and modification to these embodiment, scope of the present invention is limited by claim and equivalent thereof.
Claims (7)
1. synthesizing methanol by fluidized bed catalyst, mixture by active component presoma and binding agent obtained 150～400 degrees centigrade of lower spray-dryings and 300～450 degrees centigrade of lower calcinings in 1～3 hour, it is characterized in that, with the weight percent meter of oxide, contain in the described mixture:
The active component presoma of 30wt%～80wt%; With
The binding agent of 20wt%～70wt%,
Wherein, described binding agent is the zirconium gel,
In the molar fraction of metallic atom, contain in the described active component presoma:
The copper atom of 30～80 molar fractions;
The zinc atom of 20～40 molar fractions;
The aluminium atom of 0～15 molar fraction; With
The zirconium atom of 0～15 molar fraction.
2. synthesizing methanol by fluidized bed catalyst according to claim 1 is characterized in that, described zirconium gel is zirconium hydroxide gel or zirconyl hydroxide gel.
3. synthesizing methanol by fluidized bed catalyst according to claim 1 is characterized in that, described synthesizing methanol by fluidized bed is 0.6～1.0g/ml with the size distribution of catalyst at 20～300 μ m and bulk density.
4. the preparation method of a synthesizing methanol by fluidized bed usefulness catalyst is characterized in that, may further comprise the steps:
A) make soluble metallic salt and carbonate or bicarbonate under condition of heating and stirring, coprecipitation reaction occur, obtain the active component presoma, contain soluble copper salt, soluble zinc salt, aluminum soluble salt and solubility zirconates in the described soluble metallic salt;
B) zirconates and precipitating reagent are reacted under condition of heating and stirring, reaction is stirred and is left standstill after finishing, and obtains the zirconium gel;
C) described active component presoma is mixed with described zirconium gel, obtain mixture; With
D) with described mixture 150～400 degrees centigrade of lower spray-dryings, and 300～450 degrees centigrade of lower calcinings 1～3 hour, obtain described synthesizing methanol by fluidized bed catalyst,
Wherein, with the weight percent meter of oxide, contain the described active component presoma of 30wt%～80wt% and the described zirconium gel of 20wt%～70wt% in the described pre-composition, in the molar fraction of metallic atom, contain in the described active component presoma:
The copper atom of 30～80 molar fractions;
The zinc atom of 20～40 molar fractions;
The aluminium atom of 0～15 molar fraction; With
The zirconium atom of 0～15 molar fraction.
5. synthesizing methanol by fluidized bed according to claim 4 is characterized in that with the preparation method of catalyst, and described soluble copper salt comprises copper nitrate, Schweinfurt green or its combination,
Described soluble zinc salt comprises zinc nitrate, zinc acetate or its combination,
Described aluminum soluble salt comprises aluminum nitrate, aluminum acetate or its combination,
Described solubility zirconates comprises zirconium nitrate, acetic acid zirconium or its combination.
6. synthesizing methanol by fluidized bed according to claim 4 is characterized in that with the preparation method of catalyst, step a) in, described carbonate is sodium carbonate or potash, described bicarbonate is sodium acid carbonate or saleratus.
7. synthesizing methanol by fluidized bed according to claim 4 is characterized in that step b with the preparation method of catalyst) in,
Described zirconates is one or more in zirconyl nitrate, zirconium oxychloride, the zirconium nitrate,
Described precipitating reagent is one or more in NaOH, potassium hydroxide, sodium carbonate, potash, sodium acid carbonate or the saleratus.
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| KR102233613B1 (en) * | 2018-10-15 | 2021-03-30 | 재단법인 포항산업과학연구원 | Catalyst for water gas shift reaction in middle temperature, preparation method thereof, and hydrogen preparation method using the same |
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