CN104162447B - A kind of preparation method and application of solid catalyst - Google Patents
A kind of preparation method and application of solid catalyst Download PDFInfo
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- CN104162447B CN104162447B CN201410350670.6A CN201410350670A CN104162447B CN 104162447 B CN104162447 B CN 104162447B CN 201410350670 A CN201410350670 A CN 201410350670A CN 104162447 B CN104162447 B CN 104162447B
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Abstract
The present invention relates to a kind of preparation method of solid catalyst, and application of the solid catalyst in fatty acid ester is prepared, comprise the following steps：S1：By porous zeolite, drying is cooled to room temperature S2 at a temperature of 100~150 DEG C：The nitrate containing the one or two kinds of in aluminium, zinc, zirconium, titanium, magnesium or other active components is dissolved in deionized water, is made into corresponding solution S 3：The porous zeolite obtained in step S1 is added in the solution obtained in step S2 and carries out dipping S4：In a nitrogen environment, progress heats up obtains solid catalyst to the solid product that step S3 is obtained.This method has preparation technology simple and catalyst raw material is separated from each other the characteristics of may be recovered utilization, the characteristics of solid catalyst prepared has excellent catalytic effect and long service life, the solid catalyst that this method is prepared can be applied to prepare fatty acid methyl ester, and the yield of target product is more than 95%.
Description
Technical field
The present invention relates to environmental catalysis and biological technical field, more particularly to a kind of solid catalyst preparation method and should
With.
Background technology
Fatty acid methyl ester is yellow clear liquid (being colourless after rectifying), with a kind of gentle, distinctive smell,
Stability Analysis of Structures, without corrosivity.Fatty acid methyl ester is the raw material of widely used surfactant (SAA).From fatty acid methyl ester
Two major class surfactants can be produced by setting out, a class be by sulfonation and production MES (MES), it is another kind of
It is by being hydrogenated with production fatty alcohol.With very wide application field and purposes.
The catalyst system and catalyzing used in fatty acid methyl ester is prepared by ester exchange reaction can be divided into homogeneous catalysis system and heterogeneous
Catalyst system and catalyzing；Lot of documents is reported and production experience shows that current catalyst system and catalyzing touches and there is problems with：
1st, the separation of catalyst and product is difficult, and substantial amounts of waste liquid will be produced in last handling process and is excluded；
2nd, the efficiency of catalyst is very low.
Think ratio with current catalyst, porous supported catalyst then has catalytic activity high, can recycled, while not
Many advantages, such as in the presence of separation.
Studying more solid catalyst at present mainly has the oxide of alkalies and alkaline earth, more with micropore and mesoporous
Molecular sieve is main body, for example Chinese patent CN101148396A, CN10113873A, CN1821195A, it was recently reported that with mesoporous molecular
Sieve the preparation method of the solid catalyst for carrier；As described above, no matter that method, can surface be modified or its other party
Method introduces active component, but also usually only emphasizes active component, and have ignored shadow of the structure of carrier to catalytic activity in itself
Ring
The content of the invention
In view of the above-mentioned problems in the prior art, it is a primary object of the present invention to solve the defect of prior art,
The present invention provides a kind of preparation method and application of solid catalyst, and this method has preparation technology simply and catalyst raw material is mutual
The characteristics of mutually separately may be recovered utilization, the solid catalyst prepared by this method has excellent catalytic effect and used
The characteristics of long lifespan, meanwhile, the solid catalyst that this method is prepared can be applied to prepare fatty acid methyl ester, target product
Yield is more than 95%.
The invention provides a kind of preparation method of solid catalyst, comprise the following steps：
S1：After porous zeolite is dried 3~5 hours at a temperature of 100~150 DEG C, room is naturally cooled in drier
Temperature, and closed preservation, with standby, the porous zeolite refers to the zeolitic material with 2~5nm pore structures；
S2：By the nitrate containing the one or two kinds of in aluminium, zinc, zirconium, titanium, magnesium or other active components, it is dissolved in
In deionized water, solution corresponding thereto is made into；
S3：The porous zeolite obtained in step S1 is added in the solution obtained in step S2 and impregnated, at 30 DEG C
At a temperature of persistently stir 12~72 hours, stirring terminate after again at a temperature of 40~90 DEG C carry out solvent evaporation, obtain solid production
Thing；
S4：The solid product that step S3 is obtained in a nitrogen environment, with 2~5 DEG C/min programming rate from room temperature liter
A temperature between to 100~700 DEG C, and constant temperature after 1~6 hour at this temperature, Temperature fall in a nitrogen environment,
Obtain solid catalyst.
Optionally, the specific surface area of the porous zeolite is 400~1800m2/ g, pore volume is 0.6~4.1cm3/ g, resistance to compression
Intensity is more than 600N.
Optionally, the porous zeolite is the spherical zeolite that a diameter of porous zeolite is a diameter of 2~3mm.
Optionally, mass percent of the compound in solid catalyst containing the active component is 0.5~15%.
The present invention also provides a kind of solid catalyst prepared according to the preparation method of above-mentioned solid catalyst and prepares fat
Fatty acid methyl esters, by fatty acid ester and fatty alcohol by being mounted with the fixed bed of above-mentioned solid catalyst, in 50~120 DEG C of temperature
Under, reacted under certain air speed, reaction is collected into storage tank after terminating and carries out stratification, and fatty acid methyl is obtained after layering
Ester.
Optionally, quality hundred of the solid catalyst in the mixture of fatty acid ester, fatty alcohol and solid catalyst
Divide than being 0.5~8.0%, the molar percentage of the fatty alcohol and the fatty acid ester is 3~15: 1.
Optionally, the fatty acid ester and fatty alcohol are reacted by being mounted with the fixed bed of above-mentioned solid catalyst
When, kept the temperature at by way of microwave irradiation or heating between 50~120 DEG C.
Optionally, the fatty acid ester is the one or more in rapeseed oil, soybean oil, castor oil or palm oil.
The present invention has advantages below and beneficial effect：The present invention provides a kind of preparation method of solid catalyst and answered
Have preparation technology simple with, this method and catalyst raw material is separated from each other the characteristics of may be recovered utilization, by party's legal system
The characteristics of standby obtained solid catalyst has excellent catalytic effect and long service life, meanwhile, what this method was prepared consolidates
Body catalyst can be applied to prepare fatty acid methyl ester, and the yield of target product is more than 95%.
Embodiment
Below with reference to specific embodiment, the present invention is further illustrated.
Embodiment 1
Weigh 120g zinc nitrates (Zn (NO3)2) be dissolved in 1000ml deionized water, after full and uniform, then will
100g is immersed by 120 DEG C of porous zeolites for drying 3 hours, and porous zeolite has 2~5nm pore structures, its specific surface area
For 1000m2/ g, pore volume is 3.0cm3/ g, compression strength is more than 600N, and the porous zeolite is that a diameter of porous zeolite is
A diameter of 2~3mm spherical zeolite；
After being stirred 24 hours at 30 DEG C, 90 DEG C are evaporated and obtain the spherical sample of solid, and the spherical sample of solid is protected in nitrogen
350 DEG C are risen to 5 DEG C/min under shield, and constant temperature is after 6 hours, naturally cools to room temperature and closed preservation, obtains supported solid
Catalyst；
Above-mentioned catalyst is fitted into 200ml glass fixed bed reactors, by fixed bed by the way of microwave is heated
Be warming up to 80 DEG C, then with peristaltic pump by the mixture (mol ratio of the methanol and rapeseed oil be 3: 1) of rapeseed oil, methanol with
50ml flow velocity is pumped into fixed reaction bed reaction per hour, flows into storage tank after reactant is condensed, treats static 2 post sales, liquid
Mixture stratification, obtains fatty acid methyl ester, and its yield is 95.0%.
Embodiment 2
Weigh 140g aluminum nitrates (Al (NO3)3) be dissolved in 1000ml deionized water, after full and uniform, then will
100g is immersed by 130 DEG C of porous zeolites for drying 3 hours, and porous zeolite has 2~5nm pore structures, its specific surface area
For 1000m2/ g, pore volume is 3.0cm3/ g, compression strength is more than 600N, and the porous zeolite is spherical for a diameter of 2~~3mm's
Zeolite；
After being stirred 24 hours at 30 DEG C, 90 DEG C are evaporated and obtain the spherical sample of solid.The spherical sample of solid is protected in nitrogen
380 DEG C are risen to 10 DEG C/min under shield, and constant temperature is after 6 hours, naturally cools to room temperature and closed preservation, obtains supported solid
Catalyst；
Above-mentioned catalyst is fitted into 200ml glass fixed bed reactors, by fixed bed by the way of microwave is heated
Be warming up to 90 DEG C, then with peristaltic pump by rapeseed oil, methanol mixture (mol ratio of the methanol and the rapeseed oil is 5:
1) it is pumped into fixed reaction bed with the flow velocity of 50ml per hour to react, flows into storage tank after reactant is condensed, treat static 2 post sales,
Liquefied mixture stratification, obtains fatty acid methyl ester, and its yield is 95.5%.
Embodiment 3
Weigh 150g Titanium Nitrates (Ti (NO3)4) be dissolved in 1000ml deionized waters, after full and uniform, then by 100g
It is immersed by 130 DEG C of porous zeolites for drying 3 hours, porous zeolite has 2~5nm pore structures, its specific surface area is
1000m2/ g, pore volume is 3.0cm3/ g, compression strength is more than 600N, and the porous zeolite is a diameter of 2~3mm spherical zeolite；
After being stirred 24 hours at 30 DEG C, 90 DEG C are evaporated and obtain the spherical sample of solid.The spherical sample of solid is protected in nitrogen
480 DEG C are risen to 10 DEG C/min under shield, and constant temperature is after 6 hours, naturally cools to room temperature and closed preservation, obtains supported solid
Catalyst；
Above-mentioned catalyst is fitted into 200ml glass fixed bed reactors, by fixed bed by the way of microwave is heated
Be warming up to 90 DEG C, then with peristaltic pump by the mixture (mol ratio of the methanol and rapeseed oil be 8: 1) of rapeseed oil, methanol with
50ml flow velocity is pumped into fixed reaction bed reaction per hour, flows into storage tank after reactant is condensed, treats static 2 post sales, liquid
Mixture stratification, obtains fatty acid methyl ester, and its yield is 95%.
Embodiment 4
Weigh the nitric hydrate zirconiums of 130g five (Zr (NO3)4·5H2O) it is dissolved in 1000ml deionized waters, after full and uniform,
Then 100g is immersed by 130 DEG C of porous zeolites for drying 3 hours, porous zeolite has 2~5nm pore structures, it compares
Surface area is 1000m2/ g, pore volume is 3.0cm3/ g, compression strength is more than 600N, and the porous zeolite is a diameter of 2~3mm's
Spherical zeolite；
After being stirred 24 hours at 30 DEG C, 90 DEG C are evaporated and obtain the spherical sample of solid.The spherical sample of solid is protected in nitrogen
400 DEG C are risen to 10 DEG C/min under shield, and constant temperature is after 6 hours, naturally cools to room temperature and closed preservation, obtains supported solid
Catalyst；
Above-mentioned catalyst is fitted into 200ml glass fixed bed reactors, by fixed bed by the way of microwave is heated
Be warming up to 90 DEG C, then with peristaltic pump by rapeseed oil, methanol mixture (mol ratio for being methanol and rapeseed oil is 6: 1) with every
Hour 50ml flow velocity is pumped into fixed reaction bed reaction, and storage tank is flowed into after reactant is condensed, and after after static 2 hours, liquid is mixed
Compound stratification, obtains fatty acid methyl ester, and its yield is 97%.
Embodiment 5
Weigh 160g magnesium nitrates (Mg (NO3)2) be dissolved in 1000ml deionized waters, after full and uniform, then by 100g
It is immersed by 130 DEG C of porous zeolites for drying 3 hours, the porous zeolite has 2~5nm pore structures, its specific surface area
For 1000m2/ g, pore volume is 3.0cm3/ g, compression strength is more than 600N, and the porous zeolite is a diameter of 2~3mm spherical boiling
Stone；
After being stirred 24 hours at 30 DEG C, 90 DEG C are evaporated and obtain the spherical sample of solid.The spherical sample of solid is protected in nitrogen
450 DEG C are risen to 10 DEG C/min under shield, and constant temperature is after 6 hours, naturally cools to room temperature and closed preservation, obtains supported solid
Catalyst；
Above-mentioned catalyst is fitted into 200ml glass fixed bed reactors, by fixed bed by the way of microwave is heated
Be warming up to 90 DEG C, then with peristaltic pump by the mixture (mol ratio of the methanol and rapeseed oil be 6: 1) of rapeseed oil, methanol with
50ml flow velocity is pumped into the reaction of fixed reaction bed per hour, and storage tank is flowed into after reactant is condensed, after after static 2 hours, liquid
Mixture stratification, obtains fatty acid methyl ester, and its yield is 96%.
Embodiment 6
Weigh the nitric hydrate zirconiums of 140g five (Zr (NO3)45H2O) it is dissolved in 1000ml deionized waters, treats full and uniform
Afterwards, then 100g is immersed by 130 DEG C of porous zeolites for drying 3 hours, porous zeolite has 2~5nm pore structures, its
Specific surface area is 1000m2/g, and pore volume is 3.0cm3/g, and compression strength is more than 600N, and the porous zeolite is a diameter of 2~3mm
Spherical zeolite；
After being stirred 24 hours at 30 DEG C, 90 DEG C are evaporated and obtain the spherical sample of solid.The spherical sample of solid is protected in nitrogen
450 DEG C are risen to 10 DEG C/min under shield, and constant temperature is after 6 hours, naturally cools to room temperature and closed preservation, obtains supported solid
Catalyst；
Above-mentioned catalyst is fitted into 200ml glass fixed bed reactors, by fixed bed by the way of microwave is heated
Be warming up to 90 DEG C, then with peristaltic pump by the mixture (mol ratio of the methanol and soybean oil be 8: 1) of soybean oil, methanol with
50ml flow velocity is pumped into the reaction of fixed reaction bed per hour, and storage tank is flowed into after reactant is condensed, after after static 2 hours, liquid
Mixture stratification, obtains fatty acid methyl ester, and its yield is 97%.
Embodiment 7
Weigh 130g magnesium nitrates (Mg (NO3) 2) to be dissolved in 1000ml deionized waters, after full and uniform, then by 100g
It is immersed by 130 DEG C of porous zeolites for drying 3 hours, porous zeolite has 2~5nm pore structures, its specific surface area is
1000m2/ g, pore volume is 3.0cm3/ g, compression strength is more than 600N, and the porous zeolite is a diameter of 2~3mm spherical zeolite；
After being stirred 24 hours at 30 DEG C, 90 DEG C are evaporated and obtain the spherical sample of solid.The spherical sample of solid is protected in nitrogen
350 DEG C are risen to 10 DEG C/min under shield, and constant temperature is after 6 hours, naturally cools to room temperature and closed preservation, obtains supported solid
Catalyst；
Above-mentioned catalyst is fitted into 200ml glass fixed bed reactors, by fixed bed by the way of microwave is heated
Be warming up to 85 DEG C, then with peristaltic pump by the mixture (mol ratio of the methanol and soybean oil be 8: 1) of soybean oil, methanol with
50ml flow velocity is pumped into the reaction of fixed reaction bed per hour, and storage tank is flowed into after reactant is condensed, after after static 2 hours, liquid
Mixture stratification, obtains fatty acid methyl ester, and its yield is 95%.
Embodiment 8
Weigh 100g zinc nitrates (Zn (NO3)2) and 130g magnesium nitrates (Al (NO3)3) be dissolved in 1000ml deionized waters, treat
After full and uniform, then 100g is immersed by 130 DEG C of porous zeolites for drying 3 hours, porous zeolite has 2~5nm
Pore structure, its specific surface area is 1000m2/ g, pore volume is 3.0cm3/ g, compression strength is more than 600N, and the porous zeolite is diameter
For 2~3mm spherical zeolite；
After being stirred 24 hours at 30 DEG C, 90 DEG C are evaporated and obtain the spherical sample of solid.The spherical sample of solid is protected in nitrogen
450 DEG C are risen to 10 DEG C/min under shield, and constant temperature is after 6 hours, naturally cools to room temperature and closed preservation, obtains supported solid
Catalyst；
Above-mentioned catalyst is fitted into 200ml glass fixed bed reactors, by fixed bed by the way of microwave is heated
Be warming up to 90 DEG C, then with peristaltic pump by the mixture (mol ratio of the methanol and castor oil be 7: 1) of castor oil, methanol with
50ml flow velocity is pumped into the reaction of fixed reaction bed per hour, and storage tank is flowed into after reactant is condensed, after after static 2 hours, liquid
Mixture stratification, obtains fatty acid methyl ester, and its yield is 96%.
Embodiment 9
Weigh 140g zinc nitrates (Zn (NO3)2) and 100g magnesium nitrates (Mg (NO3)2) be dissolved in 1000ml deionized waters, treat
After full and uniform, then 100g is immersed by 130 DEG C of porous zeolites for drying 3 hours, porous zeolite has 2~5nm
Pore structure, its specific surface area 1000m2/ g, pore volume is 3.0cm3/ g, compression strength is more than 600N, and the porous zeolite is a diameter of
2~3mm spherical zeolite；
After being stirred 24 hours at 30 DEG C, 90 DEG C are evaporated and obtain the spherical sample of solid.The spherical sample of solid is protected in nitrogen
500 DEG C are risen to 10 DEG C/min under shield, and constant temperature is after 6 hours, naturally cools to room temperature and closed preservation, obtains supported solid
Catalyst；
Above-mentioned catalyst is fitted into 200ml glass fixed bed reactors, by fixed bed by the way of microwave is heated
Be warming up to 85 DEG C, then with peristaltic pump by the mixture (mol ratio of the methanol and soybean oil be 9: 1) of soybean oil, methanol with
50ml flow velocity is pumped into the reaction of fixed reaction bed per hour, and storage tank is flowed into after reactant is condensed, after after static 2 hours, liquid
Mixture stratification, obtains fatty acid methyl ester, and its yield is 97%.
Finally it should be noted that：Above-described embodiments are merely to illustrate the technical scheme, rather than to it
Limitation；Although the present invention is described in detail with reference to the foregoing embodiments, it will be understood by those within the art that：
It can still modify to the technical scheme described in previous embodiment, or which part or all technical characteristic are entered
Row equivalent substitution；And these modifications or substitutions, the essence of appropriate technical solution is departed from various embodiments of the present invention technical side
The scope of case.
Claims (3)
1. a kind of preparation method of solid catalyst, it is characterised in that comprise the following steps：
S1：After porous zeolite is dried 3~5 hours at a temperature of 100~150 DEG C, room temperature is naturally cooled in drier, and
Closed preservation is with standby, and the porous zeolite refers to the zeolitic material with 2~5nm pore structures；The porous zeolite is diameter
For 2~3mm spherical zeolite, the specific surface area of the porous zeolite is 400~1800m2/ g, pore volume is 0.6~4.1cm3/ g,
Compression strength is more than 600N；
S2：By the nitrate containing the one or two kinds of in aluminium, zinc, zirconium, titanium, magnesium or other active components, be dissolved in from
In sub- water, solution corresponding thereto is made into；
S3：The porous zeolite obtained in step S1 is added in the solution obtained in step S2 and impregnated, in 30 DEG C of temperature
Persistently stir 12~72 hours down, stirring carries out solvent evaporation at a temperature of 40~90 DEG C again after terminating, and obtains solid product；
S4：The solid product that step S3 is obtained in a nitrogen environment, 100 is risen to 2~5 DEG C/min programming rate from room temperature
A temperature between~700 DEG C, and constant temperature is after 1~6 hour at this temperature, Temperature fall, is obtained in a nitrogen environment
Solid catalyst.
2. the preparation method of solid catalyst according to claim 1, it is characterised in that the change containing the active component
Mass percent of the compound in solid catalyst is 0.5~15%.
3. solid catalyst prepared by the preparation method of solid catalyst according to claim 1 prepares fatty acid methyl ester,
Characterized in that, by fatty acid ester and fatty alcohol by being mounted with the fixed bed of above-mentioned solid catalyst, by microwave irradiation or
The mode of heating is kept the temperature at a temperature of 50~120 DEG C, is reacted under certain air speed, and reaction is collected into storage after terminating
Fatty acid methyl ester is obtained after carrying out stratification, layering in tank；
Mass percent of the solid catalyst in the mixture of fatty acid ester, fatty alcohol and solid catalyst be 0.5~
8.0%, the molar percentage of the fatty alcohol and the fatty acid ester is 3~15: 1；
The fatty acid ester is the one or more in rapeseed oil, soybean oil, castor oil or palm oil.
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| CN106750208A (en) * | 2016-12-12 | 2017-05-31 | 衡阳山泰化工有限公司 | A kind of powdery paints polyester resin special and preparation method thereof |
| BR112021000309A2 (en) | 2018-07-12 | 2021-04-06 | Sironix Renewables, Inc. | METHOD FOR FORMING A SURFACTANT, AND, COMPOUND |
| WO2021133623A1 (en) | 2019-12-23 | 2021-07-01 | Sironix Renewables, Inc. | Surfactants from aldehydes |
| US11492338B2 (en) | 2020-05-04 | 2022-11-08 | Sironix Renewables, Inc. | Furan surfactant compositions and methods |
| CN116351457A (en) * | 2023-03-07 | 2023-06-30 | 中国科学院青岛生物能源与过程研究所 | Catalyst, preparation method thereof and method for preparing 3-hydroxy propionic acid by catalyzing hydrolysis of methyl 3-methoxypropionate by using catalyst |
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