CN104437510B - A kind of CO2the preparation method of preparing methanol by hydrogenation copper-zinc-based catalyst - Google Patents
A kind of CO2the preparation method of preparing methanol by hydrogenation copper-zinc-based catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- -1 copper-zinc Chemical compound 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 239000010949 copper Substances 0.000 claims abstract description 38
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 30
- 229910052802 copper Inorganic materials 0.000 claims abstract description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000032683 aging Effects 0.000 claims description 43
- 239000007788 liquid Substances 0.000 claims description 41
- 239000000463 material Substances 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 20
- 239000000969 carrier Substances 0.000 claims description 18
- 239000011701 zinc Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 229910052725 zinc Inorganic materials 0.000 claims description 14
- 238000010009 beating Methods 0.000 claims description 11
- 239000011736 potassium bicarbonate Substances 0.000 claims description 7
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N precursor Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M NaHCO3 Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 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 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- JLDSOYXADOWAKB-UHFFFAOYSA-N Aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M Potassium bicarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229940094025 potassium bicarbonate Drugs 0.000 claims description 2
- 239000001184 potassium carbonate Substances 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 239000001187 sodium carbonate Substances 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 150000002910 rare earth metals Chemical group 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 23
- 238000002156 mixing Methods 0.000 abstract description 22
- 230000003197 catalytic Effects 0.000 abstract description 13
- 230000003993 interaction Effects 0.000 abstract description 3
- 230000001105 regulatory Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000007787 solid Substances 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- NNBFNNNWANBMTI-UHFFFAOYSA-M [4-[[4-(diethylamino)phenyl]-phenylmethylidene]cyclohexa-2,5-dien-1-ylidene]-diethylazanium;hydrogen sulfate Chemical compound OS([O-])(=O)=O.C1=CC(N(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](CC)CC)C=C1 NNBFNNNWANBMTI-UHFFFAOYSA-M 0.000 description 8
- 238000007792 addition Methods 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 101700015466 Cat-1 Proteins 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 101700021616 catA1 Proteins 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000011344 liquid material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 150000003839 salts Chemical group 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N Barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 101700021218 CAT Proteins 0.000 description 2
- 101700075228 CAT3 Proteins 0.000 description 2
- 101700086161 GCH1 Proteins 0.000 description 2
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 2
- 241000907663 Siproeta stelenes Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 101700057041 kdpQ Proteins 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 241000287882 Pavo Species 0.000 description 1
- 229910002828 Pr(NO3)3·6H2O Inorganic materials 0.000 description 1
- GTKAAVZEFUFXDD-UHFFFAOYSA-N Syntin Chemical compound C1CC1C1(C)CC1C1CC1 GTKAAVZEFUFXDD-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N TiO Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910007470 ZnO—Al2O3 Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 230000001476 alcoholic Effects 0.000 description 1
- 229910001884 aluminium oxide Inorganic materials 0.000 description 1
- OCVCVOQURVOMFR-UHFFFAOYSA-N aluminum;nitric acid Chemical compound [Al].O[N+]([O-])=O OCVCVOQURVOMFR-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 238000011030 bottleneck Methods 0.000 description 1
- 229910052599 brucite Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 235000005035 ginseng Nutrition 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011068 load Methods 0.000 description 1
- 230000000051 modifying Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000001568 sexual Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000002269 spontaneous Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing Effects 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910001929 titanium oxide Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Abstract
The invention discloses a kind of CO2The preparation method of preparing methanol by hydrogenation copper-zinc-based catalyst, copper-zinc-based catalyst is prepared by small size flow mixing device and ultrasonic wave added effect, can accurately control catalyst preparation conditions, it is easy to regulating catalyst activity presoma crystalline phase forms, thus improves catalytic performance and hydrothermal stability.Described small size flow mixing device is made up of blender and reaction tube.The catalyst being prepared by the method for the present invention, it is possible to increase the quantity of catalyst activity presoma aurichalcite, the interaction between copper zinc is strong, and reduction rear catalyst metallic copper specific surface area is high, at CO2Preparing methanol by hydrogenation reaction have high activity, methanol space-time yield and hydrothermal stability.
Description
Technical field
The present invention relates to the preparation method of a kind of methanol synthesis catalyst, be specifically related to a kind of CO2Preparing methanol by hydrogenation copper
The preparation method of zinc based catalyst.
Background technology
Along with developing rapidly of modern industry, and the continuous lifting of Global Auto owning amount, bring environmental pollution and
Extreme climate takes place frequently phenomenon, day by day causes the great attention of countries in the world.Therefore, carbon dioxide (CO2) reduce discharging be the current world
Various countries are badly in need of in the face of one of significant problem with solution.
Famous organic chemist George Euler proposes the concept of " methanol economy ", i.e. traps CO from air2, simultaneously
Utilize non-fossil energy hydrogen making, pass through CO2Hydrogenation obtains methanol, using methanol substitute fossil fuels as energy storage, combustion
Material and Synthin and downstream product be reply oil gas energy problem an effective solution route (J.Org.Chem., 2009,
74(2):487-498.).Nobel Prize in physics winner's Caro Rubia is the openest to be proposed with carbon dioxide and adds
The mode of hydrogen methanol replaces the carbon capture being in fashion now and seals up for safekeeping, it is achieved provide raw material for industry while reduction of discharging.U.S.'s carbon
Scientific Research Corp. proposes a kind of from CO2Set out and produce the three-steps process of fuel oil, with the CO in flue gas2For raw material, use
Hydrogen source needed for saline electrolysis offer.
Although in the world to CO2Preparing methanol by hydrogenation technology correlational study report is countless, but this technology wants to realize producing
Industryization is still faced with some technical bottlenecks, wherein, it is most important that the research and development of effective catalyst.CO2The chemical bond energy of molecule is high,
It is difficult to participate in chemical reaction, therefore, CO2Preparing methanol by hydrogenation reaction needs just can be smoothed out in the presence of high performance catalyst.
Conventional methanol synthetic catalyst Cu-ZnO-Al2O3For CO2In preparing methanol by hydrogenation reaction, catalytic performance is the highest.It is believed that CO
(or CO2) preparing methanol by hydrogenation Cu-ZnO base catalyst roasting before activity presoma should be copper zinc Multiple salts forms, including (Cu,
Zn)2CO3(OH)2(cuprozincite phase), (Cu, Zn)5(CO3)2(OH)6(aurichalcite).The methanol that traditional coprecipitation prepares
In synthetic catalyst roasting presoma crystalline phase based on cuprozincite mutually (J.Mol.Catal., A-Chemical, 2013,366:
48-53.), it is the active presoma of CO preparing methanol by hydrogenation, to CO2Preparing methanol by hydrogenation has certain catalytic performance, but is not
Good activity presoma.Also researcher is had to think, due to CO2Preparing methanol by hydrogenation product is attended by substantial amounts of water generate, and
Al2O3There is hydrophilic, cause catalyst to be easily subject to the impact of hydrone, as mechanical strength decline, active sites are modified
(J.Catal.,2007,249(2):185-194.).Therefore, copper-zinc-based catalyst is improved at CO2In preparing methanol by hydrogenation reaction
The research of catalytic performance be concentrated mainly on improve method for preparing catalyst and to auxiliary agent, carrier selection on, it is therefore an objective to Neng Gouyou
Effect controls CO2The formation of preparing methanol by hydrogenation catalyst activity presoma crystalline phase, improves catalyst catalytic performance and hydrothermal stability.
Summary of the invention
Goal of the invention: provide a kind of hydrothermal stability to be preferably applicable to CO2The copper zinc-base catalysis of preparing methanol by hydrogenation reaction
The preparation method of agent.
Technical scheme: the present invention mainly prepares the catalysis of copper zinc-base by small size flow mixing device and ultrasonic wave added effect
Agent, described small size flow mixing device is made up of blender and reaction tube, and described blender channel diameter is 50～2000 μm,
Described tube inner diameter is 0.5～8mm.Concrete preparation method is as follows:
(1) preparation is containing Cu, Zn and the mixed solution of auxiliary agent, is simultaneously in blender with precipitant aqueous solution and carries out
Mixing, mixed feed liquid is directly entered in the reaction tube being in Ultrasonic Radiation environment reaction, with the container collection equipped with water
Discharge product, product obtains parent through aging, washing；(2) formulation vehicle precursor solution, simultaneously enters with precipitant aqueous solution
Mixing in blender, mixed feed liquid is directly entered in the reaction tube being in Ultrasonic Radiation environment reaction, collects
Discharge product, product agitated aging, washing obtain carrier material；(3) parent is mixed making beating with carrier material, wash, filter, roast
After burning, molding, obtain catalyst.
The described mixed solution containing Cu, Zn and auxiliary agent is nitrate aqueous solution, and wherein the amount ratio of Cu/Zn material is 3/
7～7/3.
Described carrier comprises the one in aluminium oxide, zirconium oxide, titanium oxide；Corresponding support precursor is respectively nitric acid
Aluminum, zirconium nitrate and butyl titanate, the amount of the total material of carrier is 0.1～1 with the ratio of the amount of copper material in catalyst.
Described auxiliary agent comprises one or more in alkali earth metal and rare earth element, the amount of the total material of auxiliary agent with urge
In agent, the ratio of the amount of copper material is 0.05～0.1.
Described precipitant comprises in sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate
One or both mixture, precipitant concentration is 0.05～1mol/L.Precipitant in described step (1) and step (2) is permissible
Identical or different.
Blender and reaction tube are in 40～75 DEG C of environment, and the feed liquid time of staying in micro-mixer is 5～1000ms,
The feed liquid time of staying in reaction tube is 5～40min.
Described ultrasonic frequency is 20～40kHz, and ultrasonic power scope is 50～500W.
Reaction tube outlet material liquid pH controls 7～8.
Washing step is less than 10 μ S/cm for terminating with washing to electrical conductivity of solution.
Mixing making beating is carried out at 40～75 DEG C.Sintering temperature is 300～500 DEG C.
Make the catalyst prepared in aforementioned manners, live before catalyst roasting can being controlled by modulation ultrasonic frequency
Crystalline phase type in property presoma.But activity presoma crystalline phase quantity is few.
Further it was found that the quantity of activity presoma crystalline phase can be increased by following aging method:
Parent after washing is placed in hermetic container, carries out hydrothermal aging.Aging temperature is 60～80 DEG C, time aging
Between be 4～24h.After hydrothermal aging, suspension is become emerald green from blueness.
The present invention also has another embodiment, and following methods can be used to prepare copper-zinc-based catalyst:
Preparation contains Cu, Zn and the nitrate of assistant metal element and support precursor solution, same with precipitant aqueous solution
Time enter in blender and mix, mixed feed liquid is directly entered in the reaction tube being in Ultrasonic Radiation environment instead
Should, with the container collection discharge product equipped with water, product is agitated, hydrothermal aging, wash, filter, roasting, after molding, obtain
Catalyst.
Beneficial effect: the present invention combines hydrothermal aging step by small size flow mixing device and ultrasonic wave added effect, it is possible to
Accurately control catalyst preparation conditions, it is easy to regulating catalyst activity presoma crystalline phase forms.The inventive method is used to prepare
Catalyst, it is possible to increase the quantity of catalyst activity presoma aurichalcite, the interaction between copper-zinc is strong, is catalyzed after reduction
Agent metallic copper specific surface area is high, at CO2Preparing methanol by hydrogenation reaction have high activity, methanol space-time yield and hydrothermally stable
Property.
Detailed description of the invention:
Below by way of specific embodiment, the present invention is expanded on further.
Embodiment 1
Weigh 160.9g Cu (NO3)2·5H2O、115.0g Zn(NO3)2·6H2O、1.5g Mg(NO3)3·6H2O and
1.4gCa(NO3)3·4H2O is dissolved in water and is made into 0.5mol/L water solution A, prepares 0.5mol/L K2CO3Aqueous solution B, two kinds of solution
After being preheated to 70 DEG C, it is added simultaneously to A with B to fill in the container of 300mL, 70 DEG C of deionized waters and is stirred vigorously, maintaining and hold
In device, liquid pH is 7.5, continues stirring after completion of dropwise addition under conditions of temperature is 70 DEG C, and mixing time is 4h, is washed out
Obtain parent；Weigh 43.5g Al (NO3)3·9H2O is made into 0.5mol/L aqueous solution C, prepares 0.5mol/L KHCO3Aqueous solution
D, is added simultaneously to C and D under room temperature fill in 300mL deionized water container and be stirred vigorously, and maintenance liquid in containers pH is
7.0, obtain carrier, finally, parent is mixed with carrier making beating, making beating temperature is 70 DEG C, and by solid-liquid separation, solid washs extremely
Cleaning mixture electrical conductivity is 6 μ S/cm, then by solid at 100 DEG C of dry, 450 DEG C of roasting 1h, finally adds forming graphite, obtains
Cat1 catalyst.(control sample)
Embodiment 2
Weigh 160.9g Cu (NO3)2·5H2O、115.0g Zn(NO3)2·6H2O、1.5g Mg(NO3)3·6H2O and
1.4gCa(NO3)3·4H2O is dissolved in water and is made into 0.5mol/L aqueous solution I, prepares 0.5mol/L K2CO3Aqueous solution II；Two kinds of solution
After being preheated to 70 DEG C, being injected into I and II in blender by pump, two kinds of solution are in the blender that channel diameter is 1200 μm
The time of staying is 1000ms, and feed liquid out is directly entered the reaction tube that internal diameter is 8mm, and the time of staying in reaction tube is
30min, blender and reaction tube are placed in 70 DEG C of water-baths；It is 7.5 from reaction tube material liquid pH value out, and with filling 300mL
The container collection of deionized water also stirs, and continues stirring after completion of dropwise addition under conditions of temperature is 70 DEG C, and mixing time is
4h, suspension become emerald green after, washing, obtain parent；Weigh 43.5gAl (NO3)3·9H2O is made into 0.5mol/L aqueous solution
III, prepare 0.5mol/L KHCO3Aqueous solution IV, is injected into III and IV in blender by pump under room temperature, is preparing parent
Carrying out carrier under small size flow mixing device and condition of similarity to prepare, difference is, from reaction tube material liquid pH is out
7.0, liquid material is directly washed and is obtained carrier；Finally, parent mixing with carrier making beating, making beating temperature is 70 DEG C, divides by solid-liquid
From, solid washing is 6 μ S/cm to cleaning mixture electrical conductivity, then by solid at 100 DEG C of dry, 450 DEG C of roasting 1h, finally adds stone
Ink molding, obtains cat2 catalyst (control sample).
In test, it has been found that prepare if using small size flow mixing device to carry out catalyst, the catalyst obtained is lived
Property component grain size is little, and catalytic performance increases, and is better than prior art.But catalyst performance improves notable not, catalysis
Agent hydrothermal stability is poor.Therefore we by small size flow mixing device and combine ultrasonic wave added effect prepare catalyst can be more
Mending such defect, specific embodiment is as follows.
Embodiment 3
Weigh 160.9g Cu (NO3)2·5H2O、115.0g Zn(NO3)2·6H2O、1.5g Mg(NO3)3·6H2O and
1.4gCa(NO3)3·4H2O is dissolved in water and is made into 0.5mol/L aqueous solution I, prepares 0.5mol/L K2CO3Aqueous solution II；Two kinds of solution
After being preheated to 70 DEG C, being injected into I and II in blender by pump, two kinds of solution are in the blender that channel diameter is 1200 μm
The time of staying is 1000ms, and feed liquid out is directly entered the reaction tube that internal diameter is 8mm, reaction tube be placed in frequency be 40kHz and
Power is the ultrasound environments of 50W, and the time of staying in reaction tube is that 30min, blender and reaction tube are placed in 70 DEG C of water-baths；
It is 7.5 from reaction tube material liquid pH value out, and with filling the container collection of 300mL deionized water and stirring, after completion of dropwise addition
Under conditions of temperature is 70 DEG C continue stirring, mixing time is 4h, suspension become emerald green after, washing, obtain parent；Claim
Take 43.5g Al (NO3)3·9H2O is made into 0.5mol/L aqueous solution III, prepares 0.5mol/L KHCO3Aqueous solution IV, will under room temperature
III and IV is injected in blender by pump, carries out carrier system under the small size flow mixing device preparing parent and condition of similarity
Standby, difference is, is 7.0 from reaction tube material liquid pH out, and liquid material is directly washed and obtained carrier；Finally, by parent with
Carrier mixing making beating, making beating temperature is 70 DEG C, and by solid-liquid separation, solid washing is 6 μ S/cm to cleaning mixture electrical conductivity, then
By solid at 100 DEG C of dry, 450 DEG C of roasting 1h, finally add forming graphite, obtain cat3 catalyst.
The results are shown in Table 1, it is seen that embodiment 3 is prepared copper zinc-base by small size flow mixing device and ultrasonic wave added effect and is catalyzed
Agent, catalytic performance and the hydrothermal stability of catalyst all increase, and are better than cat1 catalyst prepared by prior art.By urging
Agent materialization sign, it was found that the increase of aurichalcite crystalline phase relative populations in presoma before catalyst roasting, is conducive to urging
Agent is at CO2Catalytic performance and the raising of hydrothermal stability in preparing methanol by hydrogenation reaction.In order to improve catalyst performance further,
We add hydrothermal aging and assist the optimization carrying out catalyst to prepare, and are specifically shown in embodiment 4.
Embodiment 4
Preparing catalyst by the method for similar embodiment 3, difference is, in parent preparation process, after completion of dropwise addition
Be transferred to carry out in airtight polypropylene vial aging by slurry, aging temperature is 80 DEG C, and ageing time is 4h, owing to water is spontaneous
Pressure, whole ageing process is in band pressure condition, and suspension becomes emerald green rear washing and obtains parent, other preparation process and ginseng
Numerical control system is same as in Example 3, obtains catalyst cat4.
Result from table 1, if using small size flow mixing device, and assisting ultrasonic radiation, hydrothermal aging means, energy
Enough significantly improve copper-zinc-based catalyst at CO2Activity, methanol space-time yield and hydrothermal stability in preparing methanol by hydrogenation reaction.
Embodiment 5
Weigh 92.5g Cu (NO3)2·5H2O、148.7g Zn(NO3)2·6H2O、5.8g Ba(NO3)2·6H2O and
71.6gZr(NO3)3·9H2O is dissolved in deionized water and is made into 0.1mol/L solution I, prepares 0.5mol/L NaHCO3Aqueous solution II；
After two kinds of solution are preheated to 40 DEG C, being injected into I and II in micro-mixer by pump, two kinds of solution are 500 μm at channel diameter
Micro-mixer in the time of staying be 200ms, feed liquid out is directly entered the small size reaction tube that internal diameter is 1mm, micro-instead
The time of staying of Ying Guanzhong is 10min, and micro-mixer and small size reaction tube are placed in 40 DEG C of water-baths, and small size reaction tube is placed in
Frequency is 20kHz and power is the ultrasound environments of 50W；It is 7.2 from small size reaction tube material liquid pH value out, and with filling
The container collection of 250mL deionized water also stirs, and precipitate is transferred to after completion of dropwise addition airtight hydrothermal aging in polypropylene vial,
Aging temperature is 75 DEG C, and ageing time is 20h, and suspension becomes emerald green, aging after carry out solid-liquid separation, solid washs extremely
Cleaning mixture electrical conductivity is 9 μ S/cm, then by solid at 100 DEG C of dry, 350 DEG C of roasting 2h, finally adds forming graphite, obtains
Cat5 catalyst.
Embodiment 6
Weigh 77.7g Cu (NO3)2·5H2O、83.3g Zn(NO3)2·6H2O、3.6g Ce(NO3)3·6H2O、3.6gNd
(NO3)3·6H2O and 57.2g C16H36O4Ti is dissolved in ethanol and is made into 0.05mol/L alcoholic solution I, and 0.1mol/LNaOH is water-soluble in preparation
Liquid II；After two kinds of solution are preheated to 60 DEG C, being injected into I and II in micro-mixer by pump, two kinds of solution at channel diameter are
In the micro-mixer of 1000 μm, the time of staying is 50ms, and feed liquid out is directly entered the small size reaction tube that internal diameter is 5mm,
The time of staying in small size reaction tube is 15min, and micro-mixer and small size reaction tube are placed in 60 DEG C of water-baths, and small size is anti-
Should pipe to be placed in frequency be 30kHz and power is the ultrasound environments of 200W；It is 7.0 from small size reaction tube material liquid pH value out,
And with filling the container collection of 300mL deionized water and stirring, after completion of dropwise addition, precipitate is transferred in polypropylene vial airtight
Aging, aging temperature is 60 DEG C, and ageing time is 24h, and suspension becomes emerald green, aging after carry out solid-liquid separation, solid is washed
Washing to cleaning mixture electrical conductivity is 6 μ S/cm, then by solid at 100 DEG C of dry, 400 DEG C of roasting 2h, finally adds forming graphite,
To cat6 catalyst
Embodiment 7
Weigh 138.8g Cu (NO3)2·5H2O、63.7g Zn(NO3)2·6H2O、8.2g Pr(NO3)3·6H2O is dissolved in water
It is made into 1mol/L aqueous solution I, prepares 0.5mol/L KOH-0.5mol/L KHCO3Mixed aqueous solution II；Two kinds of solution are preheated to
After 75 DEG C, being injected into I and II in micro-mixer by pump, two kinds of solution stop in the micro-mixer that channel diameter is 2000 μm
Staying the time is 800ms, and feed liquid out is directly entered the small size reaction tube that internal diameter is 5mm, stopping in small size reaction tube
Staying the time is 40min, and micro-mixer and small size reaction tube are placed in 75 DEG C of water-baths, and small size reaction tube is placed in frequency and is
20kHz and power are the ultrasound environments of 500W；It is 7.5 from small size reaction tube material liquid pH value out, and goes with filling 200mL
The container collection of ionized water also stirs, and is transferred to by precipitate in polypropylene vial airtight aging after completion of dropwise addition, and aging temperature is
75 DEG C, ageing time is 10h, and suspension becomes emerald green, and aging rear washing obtains parent；Weigh 150.1g Al (NO3)3·
9H2O is made into 1mol/L aqueous solution III, prepares 1mol/L KHCO3Aqueous solution IV, is injected into micro-mixed by III and IV by pump under room temperature
In clutch, carrying out carrier and prepare under the small size flow mixing device and condition of similarity of preparation binary parent, difference is, from
Small size reaction tube material liquid pH out is 7.0, and liquid material carries out washing obtain carrier without aging；Finally, by parent and load
Body mixing making beating, making beating temperature is 75 DEG C, and by solid-liquid separation, solid washing is 8 μ S/cm to cleaning mixture electrical conductivity, then will
Solid, at 100 DEG C of dry, 500 DEG C of roasting 1h, finally adds forming graphite, obtains cat7 catalyst.
From embodiment 5～7, different auxiliary agents to copper-zinc-based catalyst at CO2Promotion in preparing methanol by hydrogenation reaction
Effect is different, this with auxiliary agent the dispersion of catalyst surface, base strength, offer basic sites quantity relevant.
Embodiment 8
Weigh 69.4g Cu (NO3)2·5H2O、173.5g Zn(NO3)2·6H2O、10.8g La(NO3)3·6H2O and
93.8gAl(NO3)3·9H2O is dissolved in deionized water and is made into 0.02mol/L solution I, prepares 0.05mol/L Na2CO3Aqueous solution II；
After two kinds of solution are preheated to 50 DEG C, being injected into I and II in micro-mixer by pump, two kinds of solution are 50 μm at channel diameter
In micro-mixer, the time of staying is 5ms, and feed liquid out is directly entered the small size reaction tube that internal diameter is 0.5mm, in small size
The time of staying in reaction tube is 5min, and micro-mixer and small size reaction tube are placed in 50 DEG C of water-baths, and small size reaction tube is put
It is 20kHz and power is the ultrasound environments of 100W in frequency；It is 8.0 from micro-reaction tube material liquid pH value out, and with filling
The beaker of 200mL deionized water is collected and is stirred, and precipitate is transferred to after completion of dropwise addition airtight hydrothermal aging in polypropylene vial,
Aging temperature is 80 DEG C, and ageing time is 10h, and suspension gradually becomes emerald green, aging after carry out solid-liquid separation, solid is washed
Washing to cleaning mixture electrical conductivity is 7 μ S/cm, then by solid at 100 DEG C of dry, 300 DEG C of roasting 2h, finally adds forming graphite,
To cat8 catalyst.
Embodiment 9
Weigh 69.4g Cu (NO3)2·5H2O、173.5g Zn(NO3)2·6H2O、10.8g La(NO3)3·6H2O and
93.8g Al(NO3)3·9H2O is dissolved in deionized water and is made into 0.02mol/L solution A, prepares 0.05mol/L Na2CO3Aqueous solution B；
By A and B, after two kinds of solution are preheated to 50 DEG C, it is added simultaneously to A Yu B to fill in the container of 200mL, 50 DEG C of deionized waters also
Being stirred vigorously, maintaining liquid in containers pH is 7.2, and aging under stirring condition, aging temperature is 50 DEG C, and ageing time is 60min,
Carrying out solid-liquid separation after aging, solid washing is 7 μ S/cm to washing liquid electrical conductivity, then by solid 100 DEG C be dried, 300 DEG C
Roasting 2h, finally adds forming graphite, obtains cat9 catalyst.(control sample)
Active testing condition: carry out activity rating of catalyst on micro fixed-bed reactor.Catalyst grain size is 20
～40 mesh, loadings is 2mL, catalyst use before in reactor with containing 5%H2H2/N2Gaseous mixture carries out in-situ reducing, also
Former final temperature is 240 DEG C.Unstripped gas consists of H2/CO2=3/1 (volume ratio), reaction pressure is 5MPa, and air speed is 1 × 104h-1, comment
Valency temperature is 240 DEG C, and after stable reaction 4h, measurement result is initial performance.Then catalyst is at N2-H2(N is used under O atmosphere2Bubbling
100 DEG C of water), normal pressure, heat-resisting 5h at 350 DEG C, then return to above-mentioned activity rating condition, stablize the measurement result after 2h the most resistance to
Performance after heat.Product chromatographic, evaluation result is shown in Table 1, wherein, hydrothermal stability=methanol yieldAfter heat-resisting/
Methanol yieldInitially× 100%.
Table 1 catalyst is at CO2Evaluation results in preparing methanol by hydrogenation reaction
aLDHs represents (Cu2+,Zn2+)-Al3+-CO3 2-(brucite crystalline phase)；R represents (Cu, Zn)2CO3(OH)2(zinc peafowl
Stone crystalline phase)；A represents (Cu, Zn)5(CO3)2(OH)6(aurichalcite crystalline phase)；M represents (Cu)2CO3(OH)2(malachite crystalline phase)；b
IA/BRepresent before catalyst roasting in presoma x-ray diffraction pattern A crystalline phase 2 θ=27.5 ° at diffraction peak intensity and R crystalline phase 2
The ratio of diffraction peak intensity at θ=224.6 °.
In same x-ray diffraction pattern, the strength ratio double salt different from presoma of different Cu zinc double salt diffraction maximum contains
Amount ratio is proportionate.Data from table 1 it can be seen that under given reaction condition, the copper zinc-base prepared by this patent method
Catalyst is at CO2Preparing methanol by hydrogenation reaction is respectively provided with good catalytic performance and hydrothermal stability.Prepare with the tradition sedimentation method
Cat1 catalyst compare, by using the catalyst (cat2) prepared of small size flow mixing device, have higher after reduction
Ni metal specific surface area, catalyst performance obtains and improves to a certain extent.Ultrasonic wave added method is used in combination again and prepares (cat3), obtain
Active presoma aurichalcite crystalline phase dramatically increase (IA/BIncrease), malachite crystalline phase reduces, in hint presoma copper and zinc it
Between occur isomorphous substitution degree deepen, Interaction enhanced, reduction-state catalyst Cu specific surface area continue increase, catalyst
Catalytic performance and hydrothermal stability obtain constantly improve.Finally, then auxiliary water heat ageing (cat4), activity phase aurichalcite crystalline phase
Quantity and reduction-state catalyst Cu specific surface area are increased the most again, and catalyst performance is improved again, is especially catalyzed
The hydrothermal stability of agent is significantly improved.By embodiment 5～7 it can be seen that by this patent method, be catalyzed at copper zinc-base
Introducing different basic anhydride in agent, catalyst is at CO2Preparing methanol by hydrogenation reaction is respectively provided with good catalytic performance and water
Heat stability.Comparing embodiment 8 and 9, it can be seen that the catalyst cat8 using this patent method to prepare has substantially than cat9
Catalytic performance and hydrothermally stable sexual clorminance.To sum up, invention point may be summarized to be, and first, uses small size mixed flow dress
Put raising reduction-state catalyst Cu specific surface area；Secondly, by using ultrasonic assistant can control forerunner before catalyst roasting
Crystalline phase type in body, makes CO2Preparing methanol by hydrogenation activity presoma aurichalcite (A) quantity is improved, thus improves catalysis
The catalytic performance of agent.Finally, use hydrothermal aging effect, make aurichalcite (A) crystal formation well be developed, thus further
Improve the catalytic performance of catalyst, greatly enhance copper-zinc-based catalyst at CO2Water in preparing methanol by hydrogenation reaction
Heat stability.
Claims (8)
1. a CO2The preparation method of preparing methanol by hydrogenation copper-zinc-based catalyst, it is characterised in that prepare according to the following steps:
(1) preparation is containing Cu, Zn and the mixed solution of auxiliary agent, simultaneously enters in blender with precipitant aqueous solution and mixes,
Mixed feed liquid is directly entered in the reaction tube being in Ultrasonic Radiation environment reaction, and product obtains parent through aging, washing；
(2) formulation vehicle precursor solution, is simultaneously in blender with precipitant aqueous solution and mixes, and mixed feed liquid is straight
Tap into and be in the reaction tube of Ultrasonic Radiation environment reaction, product agitated aging, washing obtain carrier material；(3) by mother
Body mixes making beating with carrier material, washs, filters, roasting, after molding, obtains catalyst；
Described blender channel diameter is 50～2000 μm；Described tube inner diameter is 0.5～8mm；
Described blender and reaction tube are in 40～75 DEG C of environment, and the feed liquid time of staying in a mixer is 5～1000ms；Material
The liquid time of staying in reaction tube is 5～40min.
2. preparation method as claimed in claim 1, it is characterised in that described ultrasonic frequency is 20～40kHz, ultrasound wave merit
Rate scope is 50～500W.
3. preparation method as claimed in claim 1, it is characterised in that described ageing process is carried out in hermetic container, aging
Temperature is 60～80 DEG C, and ageing time is 4～24h.
4. preparation method as claimed in claim 1, it is characterised in that the described mixed solution containing Cu, Zn and auxiliary agent is mixed
Closing nitrate aqueous solution, wherein the amount ratio of Cu/Zn material is 3/7～7/3.
5. preparation method as claimed in claim 1, it is characterised in that described auxiliary agent comprises alkali earth metal and rare earth unit
One or more in element, the amount of the total material of auxiliary agent is 0.05～0.1 with the ratio of the amount of copper material in catalyst.
6. preparation method as claimed in claim 1, it is characterised in that described support precursor is respectively aluminum nitrate, zirconium nitrate
And butyl titanate, the amount of the total material of carrier is 0.1～1 with the ratio of the amount of copper material in catalyst.
7. preparation method as claimed in claim 1, it is characterised in that described precipitant comprise sodium hydroxide, potassium hydroxide,
One or both mixture in sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, precipitant concentration is 0.05～1mol/L.
8. a CO2The preparation method of preparing methanol by hydrogenation copper-zinc-based catalyst, it is characterised in that preparation is containing Cu, Zn and auxiliary agent
The nitrate of metallic element and support precursor solution, be simultaneously in blender with precipitant aqueous solution and mix, mixed
Feed liquid after conjunction is directly entered in the reaction tube being in Ultrasonic Radiation environment reaction, product is agitated, hydrothermal aging, washing,
After filtration, roasting, molding, obtain catalyst；
Described blender channel diameter is 50～2000 μm；Described tube inner diameter is 0.5～8mm；
Described blender and reaction tube are in 40～75 DEG C of environment, and the feed liquid time of staying in a mixer is 5～1000ms；Material
The liquid time of staying in reaction tube is 5～40min.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410604941.6A CN104437510B (en) | 2014-10-30 | A kind of CO2the preparation method of preparing methanol by hydrogenation copper-zinc-based catalyst | |
| US14/928,345 US10010875B2 (en) | 2014-10-30 | 2015-10-30 | Method for preparing copper-zinc-based catalyst used in synthesis of methanol through CO2 hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410604941.6A CN104437510B (en) | 2014-10-30 | A kind of CO2the preparation method of preparing methanol by hydrogenation copper-zinc-based catalyst |
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| Publication Number | Publication Date |
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| CN104437510A CN104437510A (en) | 2015-03-25 |
| CN104437510B true CN104437510B (en) | 2017-01-04 |
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Address after: 100728 Beijing, Chaoyangmen, North Street, No. 22, No. Patentee after: China Petroleum & Chemical Corp. Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Address before: 100728 Beijing, Chaoyangmen, North Street, No. 22, No. Patentee before: China Petroleum & Chemical Corp. Patentee before: Nanhua Group Research Institute |