CN109046361A - A kind of fatty alcohol TERTIARY AMINATING CATALYST and the preparation method and application thereof - Google Patents
A kind of fatty alcohol TERTIARY AMINATING CATALYST and the preparation method and application thereof Download PDFInfo
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- CN109046361A CN109046361A CN201810984067.1A CN201810984067A CN109046361A CN 109046361 A CN109046361 A CN 109046361A CN 201810984067 A CN201810984067 A CN 201810984067A CN 109046361 A CN109046361 A CN 109046361A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The present invention provides a kind of fatty alcohol TERTIARY AMINATING CATALYST and the preparation method and application thereof.Specifically different metal oxides are pre-mixed according to CuO:NiO:ZnO:MgO=0.3 ~ 0.75:0.013 ~ 0.13:0 ~ 0.25:0 ~ 0.25 molar ratio, addition accounts for the dispersing agent of 1 ~ 10% mass percent of metal oxide sum and 10 ~ 30% deionized waters are ground 2 ~ 6 hours, non-loaded type O composite metallic oxide catalyst is prepared through 100 ~ 120 DEG C of drying, through hydrogen reducing for being catalyzed the aminating reaction of fatty alcohol under condition of normal pressure.The introducing of low molecular weight polycarboxylic acids and its esters dispersing agent, reduce the grinding viscosity of preparation process metal oxide, improve even particulate dispersion degree between system each component, it effectively prevents catalystic converter system from forming the generation of catalyst agglomeration analysis copper phenomenon because stirring and recycling, improves catalyst activity and selectivity.Fatty alcohol conversion is up to 99%, fat tertiary amine content > 95%, catalyst recovery yield > 98%, and catalyst preparation process is simple, time-consuming short, energy conservation and environmental protection, normal pressure catalytic performance are good.
Description
Technical field
The invention belongs to chemical fields, and in particular to a kind of preparation method and application of fatty alcohol amination catalysis.
Background technique
For the Study on Catalytic Amination of Alcohols of alcohol, the key of reaction is the selection of catalyst.Therefore, the emphasis of research is concentrated mainly on pair
In the development of catalysts.Catalytic amination reaction catalyst used is mostly composite catalyst, with a kind of metallic element
Based on, other auxiliary elements are added, can be carrier or non-carrier, used carrier can be Al2O3、SiO2, diatomite,
Molecular sieve etc., the difference of constituent content contained by different preparation condition and catalyst all will affect the activity and selection of catalyst
Property.
For a catalyst system, catalytic performance is affected by many factors, wherein most importantly major catalyst is really
It is fixed.The catalyst that alcohol aminating reaction reported in the literature uses mostly is the catalyst system with Ni and Cu for main catalytic active component.Beauty
Prepared by tertiary amine to alcohol amination catalysis reaction using nickel catalyst carried in state patent US 3976697.United States Patent (USP) US
4442306 utilize copper formate Cu (CHO)2·4H2O is major catalyst, using calcium hydroxide or barium hydroxide or potassium carbonate as co-catalysis
The composite catalyst catalysis binary of agent, unitary or polyalcohol, especially fatty alcohol and there is the secondary of identical or different substituent group
Amine, especially effumability amine produce tertiary amine.China Patent Publication No. is in CN100357024C by copper nitrate, chromic nitrate and the
Three component lanthana La2O3, cobalt oxide or nickel oxide metal nitrate aqueous solution mixing or by copper nitrate, chromic nitrate and third
The aqueous solution of component metals nitrate is mixed with diatomite or 4A Zeolite support, obtains metal oxide supported type catalyst.Patent
Publication No. CN1923362A introduce use copper oxide: zinc oxide: magnesia: nickel oxide: carrier by 0.3 ~ 1.0:0 ~ 1.0:0 ~
The mixing of the molar ratio of 1.0:0 ~ 1.0 prepares catalyst using coprecipitation, and carrier selects diatomite or calcium carbonate.Tan's equality is with carbon
Sour calcium is carrier, is prepared for Cu-Ni-Ba ternary amination catalysis with coprecipitation.
The method for preparing fatty alcohol amination catalysis using co-precipitation usually first leads to the soluble nitrate of each metal
Heating, alkali tune coprecipitation method are crossed, then the step such as calcines, be ground up, sieved through aging, standing, filtering, drying, 300-500 DEG C
Suddenly, preparation process is cumbersome, and time-consuming, needs high-temperature roasting, it is desirable that condition is harsh.Unsupported catalyst catalytic activity is high, Zhang Wen
The reports such as gold press 1:(0.1 ~ 0.3 using Cu-Zn-Mg-Ni): (0.1 ~ 0.3): the mol ratio combination preparation of (0.01 ~ 0.06)
Unsupported catalyst, since metallic copper ratio is up to 70%, analysis copper phenomenon seriously affects the heat transfer efficiency of reaction in practical application,
Aminating reaction process is caused to be difficult to carry out.
Summary of the invention
In order to solve the problems existing in the prior art, the present invention provides a kind of fatty alcohol TERTIARY AMINATING CATALYST and preparation method thereof
With application.
A kind of fatty alcohol TERTIARY AMINATING CATALYST, is made of metal oxide and dispersing agent, and wherein copper oxide accounts for metal oxidation
The 30-75% of object, remaining metal oxide are one or more of nickel oxide, zinc oxide and magnesia, and wherein dispersing agent is metal
The 1-10% of oxide mass.
Wherein, the dispersing agent is low molecular weight polycarboxylic acids and its salt, and viscosity average molecular weigh range is 4000-8000.
The preparation method of above-mentioned fatty alcohol TERTIARY AMINATING CATALYST, is made by following steps: (1) by metal oxide according to rubbing
You mix than CuO:NiO:ZnO:MgO=0.3 ~ 0.75:0.013 ~ 0.13:0 ~ 0.25:0 ~ 0.25；(2) addition dispersing agent and certain
The deionized water of amount is ground, drying prepares non-loaded type O composite metallic oxide catalyst.
Wherein, the dispersing agent is low molecular weight polycarboxylic acids and its salt, and dispersing agent viscosity average molecular weigh distribution is
4000~8000；Accounting for the total mass percent of metal oxide is 1 ~ 10%.
Wherein, milling time is 2 ~ 6 hours in the step (2)；Drying temperature is 100-120 DEG C.
Wherein, it is 10 ~ 40% that the step (2) intermediate ion water additive amount, which accounts for metal oxide mass percent,.
The application of above-mentioned fatty alcohol TERTIARY AMINATING CATALYST, under condition of normal pressure, reaction temperature is 190 ~ 230 DEG C, catalyst quilt
It is catalyzed dimethylamine after reduction and fatty alcohol carries out alcohol radical tertiary ammonia.
Wherein, the catalyst reduction is to use hydrogen reducing using under hydrogen environment.
Wherein, the catalyst amount is the 0.5 ~ 3.5% of fatty alcohol quality.
Wherein, the fatty alcohol is C12~C16 One or more of fatty alcohol.
Beneficial effects of the present invention:
1. being directly mixed with non-loaded type composite catalyzing using the metal oxide of Cu, Ni, Zn, Mg by addition dispersing agent
Agent, each component disperse evenly and stably, and catalytic performance is good；
2. the addition of polycarboxylic acids and its esters dispersing agent reduces the grinding viscosity of metal oxide mixed system, reduces water
Dosage, improve the stability and catalytic activity of catalyst mixed component；
3. catalyst preparation process is simple and convenient to operate, is time-consuming short；
4. catalyst preparation process is generated without waste water, energy conservation and environmental protection.
Detailed description of the invention
Fig. 1 is that the SEM of 1 catalyst of comparative example schemes, catalyst surface metal oxide out-of-flatness in figure, is between each component
Coherent condition, dispersion is uneven, and specific surface area is small.
Fig. 2 is that the SEM of 3 catalyst of embodiment schemes, and metal oxide component is identical as comparative example 1 in catalyst, addition point
After powder, catalyst structure is compact, surfacing, and relatively uniform, large specific surface area, excellent catalytic effect are dispersed between each component.
Specific embodiment
In order to further illustrate essentiality content of the invention, it is illustrated in connection with specific embodiments, needs to explain
, the content of present invention includes but are not limited to following embodiment.
Embodiment 1
It will be put into ball mill after 16g CuO and 1g NiO premixing, is separately added into 1.2g polyacrylic acid sylvite and 5g deionized water
Grinding 2 hours, 110 DEG C dry to obtain non-loaded composite catalyst, wherein composite catalyst partial size D50=5 μm, D90=15 μm.
150g n-dodecanol and the above-mentioned catalyst of 4.5g are added in four-hole boiling flask, after nitrogen purges 20min, is warming up to
190 DEG C, while it being passed through hydrogen and dimethylamine gas, control hydrogen flowing quantity 200mL/min, dimethylamine gas flow 100mL/min.
The water that reaction generates brings water segregator into, and reaction 3h is continuously heating to 210 DEG C and reacts 2 hours, and dimethyl is steamed to obtain outside negative pressure
Base tertiary amine, tertiary amine content 95.7%, catalyst recovery yield 98.8%.
Embodiment 2
16gCuO, 1gNiO and 5gZnO are mixed, 1.6g polyacrylic acid is separately added into and 3g deionized water is ground 4 hours, 115 DEG C
Drying, composite catalyst partial size D50=6 μm, D90=14 μm.
150g tetradecanol and the above-mentioned catalyst of 1.5g are added in four-hole boiling flask, after nitrogen purges 20min, is warming up to
190 DEG C, while it being passed through hydrogen and dimethylamine gas, control hydrogen flowing quantity 200mL/min, dimethylamine gas flow 100mL/min.
The water that reaction generates brings water segregator into, and reaction 2h is continuously heating to 210 DEG C and reacts 2 hours, and dodecyldimethylamine is steamed to obtain outside negative pressure
Base tertiary amine, tertiary amine content 96.0%, catalyst recovery yield 98.1%.
Embodiment 3
16gCuO, 1gNiO and 2gMnO are mixed, 1.5g polyacrylic acid sodium salt is separately added into and 4g deionized water is ground 3 hours,
110 DEG C of drying, composite catalyst partial size D50=5 μm, D90=14 μm.
The positive hexadecanol of 150g and the above-mentioned catalyst of 1.5g are added in four-hole boiling flask, reacts 5 hours, other operating conditions are same
Embodiment 2, hexadecyldimethyl benzyl ammonium tertiary amine content are 96.8%, catalyst recovery yield 98.4%.
Embodiment 4
16gCuO, 1gNiO, 5gZnO and 2gMgO are mixed, 1.8g ammonium polyacrylate salt and 4g deionized water grinding 4 are separately added into
Hour, 115 DEG C of drying, composite catalyst partial size D50=5 μm, D90=12 μm.
150g n-dodecanol and the above-mentioned catalyst of 3.0g are added in four-hole boiling flask, with embodiment 1, tertiary amine contains other conditions
Amount is 97.1%, catalyst recovery yield 98.7%.
Embodiment 5
110g n-dodecanol and 40g tetradecanol are added in four-hole boiling flask, catalyst preparation and other operating conditions are the same as implementation
Example 4, tertiary amine content 97.4%, catalyst recovery yield 98.5%.
Embodiment 6
70g n-dodecanol and the positive hexadecanol of 80g, catalyst preparation and the same embodiment of other operating conditions are added in four-hole boiling flask
2, tertiary amine content 96.1%, catalyst recovery yield 98.7%.
Comparative example 1
16gCuO, 1gNiO and 2gMnO are mixed, 15g deionized water is added and grinds 6 hours, 110 DEG C of drying, compound to urge after filtering
Agent partial size D50=10 μm, D90=22 μm.
150g n-dodecanol and the above-mentioned catalyst of 4.5g are added in four-hole boiling flask, with embodiment 3, tertiary amine contains other conditions
Amount is 82.4%, catalyst recovery yield 88.2%.
Comparative example 2
16gCuO, 1gNiO, 5gZnO and 2gMgO are mixed, 16g deionized water is added and grinds 4 hours, 115 DEG C of drying after filtering,
Composite catalyst partial size D50=9 μm, D90=21 μm.
150g n-dodecanol and the above-mentioned catalyst of 3.0g are added in four-hole boiling flask, with embodiment 4, tertiary amine contains other conditions
Amount is 85.8%, catalyst recovery yield 90.2%.
1 catalyst of table is to fatty alcohol catalyzing amination results and recycles number contrast table
Claims (10)
1. a kind of fatty alcohol TERTIARY AMINATING CATALYST, which is characterized in that be made of metal oxide and dispersing agent, wherein copper oxide accounts for
The 30-75% of metal oxide, remaining metal oxide is one or more of nickel oxide, zinc oxide and magnesia, wherein dispersing
Agent is the 1-10% of metal oxide quality.
2. fatty alcohol TERTIARY AMINATING CATALYST according to claim 1, which is characterized in that the dispersing agent is low molecular weight
Polycarboxylic acids and its salt, viscosity average molecular weigh range are 4000-8000.
3. a kind of preparation method of fatty alcohol TERTIARY AMINATING CATALYST described in claim 1, which is characterized in that by following steps system
: (1) by metal oxide according to molar ratio CuO:NiO:ZnO:MgO=0.3 ~ 0.75:0.013 ~ 0.13:0 ~ 0.25:0 ~ 0.25
Mixing；(2) add dispersing agent and a certain amount of deionized water it is ground, drying prepare non-loaded type composite metal oxide catalyst
Agent.
4. method for preparing catalyst according to claim 3, which is characterized in that the dispersing agent is the poly- carboxylic of low molecular weight
Acid and its salt, dispersing agent viscosity average molecular weigh distribution are 4000 ~ 8000；Account for the total mass percent of metal oxide be 1 ~
10%。
5. catalysis preparation method according to claim 3, which is characterized in that milling time is 2 ~ 6 in the step (2)
Hour；Drying temperature is 100-120 DEG C.
6. catalysis preparation method according to claim 3, which is characterized in that described step (2) the intermediate ion water additive amount
Accounting for metal oxide mass percent is 10 ~ 40%.
7. the application of fatty alcohol TERTIARY AMINATING CATALYST described in a kind of claim 1, which is characterized in that under condition of normal pressure, reaction temperature
Degree is 190 ~ 230 DEG C, and catalyst is catalyzed dimethylamine after being reduced and fatty alcohol carries out alcohol radical tertiary ammonia.
8. application according to claim 7, which is characterized in that the catalyst reduction is to use using under hydrogen environment
Hydrogen reducing.
9. application according to claim 7, which is characterized in that the catalyst amount be fatty alcohol quality 0.5 ~
3.5%。
10. application according to claim 7, which is characterized in that the fatty alcohol is C12~C16 Fatty alcohol in one
Kind or more.
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| US4409399A (en) * | 1981-12-09 | 1983-10-11 | Millmaster Onyx Group, Inc. | Process for producing aliphatic amines |
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| CN1792442A (en) * | 2006-01-06 | 2006-06-28 | 中国日用化学工业研究院 | Catalyst for preparing fatty tertiary amine, prepn. method and application thereof |
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