CN104549238B - Hydrofining crude terephthalic acid catalyst and its preparation method - Google Patents
Hydrofining crude terephthalic acid catalyst and its preparation method Download PDFInfo
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- CN104549238B CN104549238B CN201310512631.7A CN201310512631A CN104549238B CN 104549238 B CN104549238 B CN 104549238B CN 201310512631 A CN201310512631 A CN 201310512631A CN 104549238 B CN104549238 B CN 104549238B
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Abstract
The present invention relates to hydrofining crude terephthalic acid catalyst and its preparation method, mainly solve the problem of catalyst heat endurance present in prior art is poor, the present invention is by using hydrofining crude terephthalic acid catalyst, the catalyst includes carrier and active component, the active component is palladium, the weight/mass percentage composition of palladium is the 0.2 ~ 1.0% of catalyst dry weight, it is characterized in that technical scheme of the carrier for the activated carbon after microwaved and ultrasonication, the technical problem is preferably solved, available in hydrofining crude terephthalic acid production.
Description
Technical field
The present invention relates to hydrofining crude terephthalic acid catalyst and its preparation method.
Background technology
P-phthalic acid, is commonly called as PTA, is synthesis polyethylene terephthalate（PET）Base stock.Support type
Pd/carbon catalyst is applied to the refined of crude terephthalic acid, the p -carboxybenzaldehyde in crude terephthalic acid（Abbreviation 4-CBA）Deng
Impurity carries out hydrogenation and is changed into after other compounds, then using the method for crystallization come separating-purifying.Due to Pd/carbon catalyst
Using single active constituent, so distribution situation of the Metal Palladium on carrier, the influence to catalyst performance is very big.
Because terephthalic acid (TPA) hydrofining reaction process is a first order reaction, reaction speed is fast, anti-in course of reaction
The inside for answering thing to be difficult to be penetrated into catalyst granules is reacted, and this allows for active metal inside particle due to steric hindrance shadow
Ring, not reaching the reactant molecule component being relatively large in diameter can not play a role.Now, the active metal of outer surface is shown
High catalytic activity.For the consideration for making full use of noble metal, usual Pd/carbon catalyst makes eggshell type, that is, allows active constituent
Palladium basic load is in the surface of carrier.The surface area that palladium is contacted with reactant is bigger, and activity is also better.Eggshell type active constituent point
The catalyst of cloth has higher hydrogenation catalyst ability than being distributed the catalyst of wider range.Terephthalic acid (TPA) hydrofinishing is usual
Reaction pressure is 6.5 ~ 8.5MPa, and reaction temperature is progress under the conditions of 250 ~ 290 DEG C, and the crystal grain of palladium is grown up unavoidably, just
Under normal reaction condition, the crystal grain of the inactivation mainly palladium of catalyst is grown up, the terephthalic acid (TPA) hydrofinishing of commercial inactivation
Palladium carbon catalyst, palladium crystal grain can grow up to more than 20nm, and the palladium crystal grain of fresh catalyst is between 2 ~ 5nm；In commercial Application
It is faster that the crystal grain of middle palladium is grown up, then the normal service life of catalyst is then shorter.The shortening of the service life of catalyst is not only
The waste of the palladium carbon catalyst of costliness is caused, and factory can be caused because more catalyst changeout heavy economic losses.
A.V.Romanenko et al. proposes the method that Ru is added in active component（Influence of ruthenium
addition on sintering of carbon-supported palladium, Applied Catalysis A:
General 227 (2002) 117-123）, as a result show that Ru addition improves the anti-caking power of catalyst, urged so as to improve
The heat endurance of agent；But Ru price is also more expensive than Pd, while Ru addition improves what terephthalic acid (TPA) phenyl ring was hydrogenated
Risk, United States Patent (USP) US6753290（Catalytic composition, method for manufacturing
thereof and method for the purification of terephthalic acid）Also there is similar report.
United States Patent (USP) US4,892,972（Purification of crude terephthalic acid）By using Pd/C and Rh/
C double-layer catalyst, Pd and Rh ratio are 10:1 is used for hydrofining crude terephthalic acid, as a result finds its catalyst life
It is significantly improved, Rh crystal grain is difficult to grow up；But Rh price is ten times of Pd, therefore is not applied in practice.
The content of the invention
One of technical problems to be solved by the invention are the problem of catalyst heat endurance present in prior art are poor,
A kind of new hydrofining crude terephthalic acid catalyst is provided, the hydrofinishing that the catalyst is used for crude terephthalic acid is anti-
Should, the characteristics of heat-resistant stability with palladium is high.
The two of the technical problems to be solved by the invention are the preparations of the catalyst corresponding with one of above-mentioned technical problem
Method.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：Hydrofining crude terephthalic acid
Catalyst, the catalyst includes carrier and active component, and the active component is palladium, and the weight/mass percentage composition of palladium is catalyst
The 0.2 ~ 1.0% of dry weight, the carrier is the activated carbon after microwaved and ultrasonication.
In above-mentioned technical proposal, described activated carbon is preferably at least one of ature of coal charcoal, carbo lignius or fruit shell carbon.Institute
The fruit shell carbon stated preferably coconut husk charcoal.Described coconut husk charcoal is preferably 800~1600m than surface2/ g, pore volume is preferably 0.35
~0.80ml/g.
To solve the two of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：The skill of one of above-mentioned technical problem
The preparation method of catalyst described in art scheme, including step once：
（1）Activated carbon is mixed with alkaline compound solution, then drying obtains precursor carrier I；
（2）To precursor carrier I microwave treatments, precursor carrier II is obtained；
（3）Precursor carrier II is immersed in water through ultrasonication, be then washed to cleaning solution into it is neutral, be dried to obtain and urge
Agent carrier；
（4）The pH value for adjusting the containing palladium compound aqueous solution by alkali compounds obtains palladium maceration extract to 1 ~ 10；
（5）The catalyst carrier is mixed with palladium maceration extract, catalyst precarsor i is obtained；
（6）Ageing, obtains catalyst precarsor ii；
（7）Compound state palladium is reduced to simple substance palladium with reducing agent, catalyst precarsor iii is obtained；
（8）Washing removes the impurity in catalyst precarsor iii, obtains described catalyst.
In above-mentioned technical proposal, step（1）Described in alkali compounds preferably be selected from alkali metal hydroxide, alkali metal carbon
At least one of hydrochlorate or ammonia, more preferably alkali carbonate, alkali carbonate more preferably sodium carbonate or potassium carbonate.Step
（1）The alkaline compound solution, the solvent of use is not particularly limited, as long as the alkali compounds can be dissolved,
Those solvents of obtained alkaline solution are used equally for the present invention, but preferably water.The concentration of the alkaline compound solution is preferred
0.1 ~ 10wt%, most preferably 1 ~ 5wt%；The ratio between the alkaline compound solution and activated carbon volume are preferably（2~4）：1；Immersion
Time preferably 10 ~ 120min.
In above-mentioned technical proposal, step（2）The microwave output power is preferably 600 ~ 2000W, most preferably 8000 ~
1200W；Frequency is 2450MHz；Processing time is preferably 1 ~ 60min, most preferably 5 ~ 30min.
In above-mentioned technical proposal, step（3）The ultrasonic power output preferably 100 ~ 2000W, more preferably 80 ~
1000W, most preferably 100 ~ 300W；Ultrasonic treatment time preferably 1 ~ 60min, more preferably 15 ~ 40min.Frequency is preferably
40KHz, the volume of water is 1 ~ 6 times of precursor carrier II, preferably 2 ~ 4 times.
Above-mentioned technical proposal, step（4）The alkali compounds be preferably alkali metal hydroxide, alkali carbonate or
At least one of ammonia, most preferably alkali carbonate.Sodium carbonate is most common, generally the least expensive, therefore the most preferred sodium carbonate.Carbon
Sour sodium can be used with fixed form, but preferably be used in the form of aqueous sodium carbonate.It is 5 that the concentration of aqueous sodium carbonate is excellent ~
15wt%, more preferably 10wt%.Described containing palladium compound preferably is selected from palladium nitrate, palladium, chlorine palladium acid and its salt and the ammonia of dichloro four
Close at least one of palladium, preferably chlorine palladium acid.Described pH is preferably 3 ~ 7.Step（5）The catalyst carrier and palladium maceration extract
Hybrid mode is not particularly limited, for example, for dipping or can spray, but preferred dipping, and the volume of maceration extract is preferably catalyst
0.3 ~ 2.0 times of carrier bulk, most preferably more preferably 0.3 ~ 0.8 times, 0.52 times.Step（6）The time of the ageing is preferred
For 8 ~ 48 hours, more preferably 24 hours.
In above-mentioned technical proposal, on step（7）The specific reducing condition such as middle reducing agent and reductant concentration, recovery time
It is not the key problem in technology of the present invention, those skilled in the art will know that how compound state palladium to be reduced into simple substance palladium with reducing agent.Example
At least one of the optional use hydrogen of reducing agent, formic acid, formaldehyde or formates are reduced as mentioned.Described formates can be
The alkali metal salt of ammonium formate, formic acid, and financially sodium formate is the most frequently used in the alkali metal salt of formic acid.When using sodium formate
During for reducing agent, aqueous sodium formate solution mass percent concentration is preferably 5 ~ 10%, and reduction temperature is preferably 30 ~ 120 DEG C, more excellent
60 ~ 100 DEG C are selected, the recovery time is preferably 0.5 ~ 8 hour, the volume of aqueous sodium formate solution is preferably the 2 ~ 4 of catalyst precarsor ii
Times.
The Palladium Content in Catalyst of the embodiment of the present invention and comparative example is determined using ICP-AES.
Catalyst thermal stability determination：
By catalyst in N2Under protection, it is calcined 8 hours at 300 ~ 500 DEG C, is subsequently cooled to room temperature.Use x-ray diffractometer
（XRD）The catalyst average crystal grain size surveyed after roasting, can be calculated with Debye-Scherrer formula.
Scherrer formula：Dhkl=k λ/β cos θ, wherein, Dhkl is along perpendicular to crystal face（hkl）The crystal grain in direction is straight
Footpath, k is Scherrer constants（Usually 0.89）, λ is incident X-rays wavelength（Cuka wavelength is 0.15406nm, Cuka1
Wavelength is 0.15418nm.）, θ is Bragg diffraction angle（°）, β is the peak width at half height of diffraction maximum（rad）.Under equal conditions, catalysis
The heat endurance of the smaller then catalyst of agent average crystal grain is better；The heat that forward backward averaging crystal grain changes smaller then catalyst is calcined simultaneously
Stability is also better.
The key problem in technology of the inventive method is the carrier of catalyst of the present invention for after microwaved and ultrasonication
Activated carbon.Using catalyst of the present invention, after 300 DEG C are handled 8 hours, average crystal grain size essentially unchangedization, even in high temperature 500
DEG C processing 8 hours, tranquil grain size achieves preferable technique effect also in below 6nm.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
Weigh 50 gram of 4~8 mesh, sheet cocoanut active charcoal（It is 1100m than surface2/ g, pore volume is 0.52ml/g）It is immersed in
In 3wt% aqueous sodium carbonates, the ratio between volume and activated carbon volume of aqueous sodium carbonate are 3:1, soak time is 30min, so
Drying obtains precursor carrier I afterwards；By above-mentioned precursor carrier I power output be 1000W, frequency for 2450MHz micro-wave oven in
Processing 5min obtains precursor carrier II；Then precursor carrier II is immersed in water, the volume of water is the 3 of precursor carrier II volumes
Times, it is then 200W in power, then frequency is washed with water to cleaning solution in handle 30min in 40KHz ultrasonoscope
Property, obtain catalyst carrier after drying.
The preparation of palladium maceration extract：1.25 grams of 20wt% containing palladium chlorine palladium aqueous acid is weighed, it is water-soluble with 10wt% sodium carbonate
Regulation chlorine palladium aqueous acid pH to 5.5 is added dropwise in liquid while stirring, then adds water and is settled to 26ml, is uniformly mixing to obtain palladium dipping
Liquid.
Said catalyst carrier is immersed in palladium maceration extract, is aged 24 hours, obtains catalyst precarsor ii；It is in temperature
At 80 DEG C, with 8wt% aqueous sodium formate solution reducing catalyst precursor ii, recovery time 60min, the volume of aqueous sodium formate solution
For 3 times of catalyst precarsor ii volumes, catalyst precarsor iii is obtained.Catalyst precarsor iii is washed with water to cleaning solution use
AgNO3Detection is without Cl-Untill, it is dried to obtain required catalyst.By the catalyst of gained under nitrogen protection respectively 300 DEG C,
400 DEG C, the heat endurance of 500 DEG C of roastings, 8 hours investigation catalyst.
For ease of comparing, the main preparation condition of catalyst agent is listed in table 1, catalyst analysis data are listed in table 2.
【Embodiment 2】
Weigh 50 gram of 4~8 mesh, sheet cocoanut active charcoal（It is 1100m than surface2/ g, pore volume is 0.52ml/g）It is immersed in
In 3wt% aqueous sodium carbonates, the ratio between volume and activated carbon volume of aqueous sodium carbonate are 3:1, soak time is 30min, so
Drying obtains precursor carrier I afterwards；By above-mentioned precursor carrier I power output be 1000W, frequency for 2450MHz micro-wave oven in
Processing 10min obtains precursor carrier II；Then precursor carrier II is immersed in water, the volume of water is precursor carrier II volumes
3 times, be then 200W in power, then frequency is washed with water to cleaning solution in handle 30min in 40KHz ultrasonoscope
Property, obtain catalyst carrier after drying.
The preparation of palladium maceration extract：1.25 grams of 20wt% containing palladium chlorine palladium aqueous acid is weighed, it is water-soluble with 10wt% sodium carbonate
Regulation chlorine palladium aqueous acid pH to 5.5 is added dropwise in liquid while stirring, then adds water and is settled to 26ml, is uniformly mixing to obtain palladium dipping
Liquid.
Said catalyst carrier is immersed in palladium maceration extract, is aged 24 hours, obtains catalyst precarsor ii；It is in temperature
At 80 DEG C, with 8wt% aqueous sodium formate solution reducing catalyst precursor ii, recovery time 60min, the volume of aqueous sodium formate solution
For 3 times of catalyst precarsor ii volumes, catalyst precarsor iii is obtained.Catalyst precarsor iii is washed with water to cleaning solution use
AgNO3Detection is without Cl-Untill, it is dried to obtain required catalyst.By the catalyst of gained under nitrogen protection respectively 300 DEG C,
400 DEG C, the heat endurance of 500 DEG C of roastings, 8 hours investigation catalyst.
For ease of comparing, the main preparation condition of catalyst agent is listed in table 1, catalyst analysis data are listed in table 2.
【Embodiment 3】
Weigh 50 gram of 4~8 mesh, sheet cocoanut active charcoal（It is 1100m than surface2/ g, pore volume is 0.52ml/g）It is immersed in
In 3wt% aqueous sodium carbonates, the ratio between volume and activated carbon volume of aqueous sodium carbonate are 3:1, soak time is 30min, so
Drying obtains precursor carrier I afterwards；By above-mentioned precursor carrier I power output be 1000W, frequency for 2450MHz micro-wave oven in
Processing 15min obtains precursor carrier II；Then precursor carrier II is immersed in water, the volume of water is precursor carrier II volumes
3 times, be then 200W in power, then frequency is washed with water to cleaning solution in handle 30min in 40KHz ultrasonoscope
Property, obtain catalyst carrier after drying.
The preparation of palladium maceration extract：1.25 grams of 20wt% containing palladium chlorine palladium aqueous acid is weighed, it is water-soluble with 10wt% sodium carbonate
Regulation chlorine palladium aqueous acid pH to 5.5 is added dropwise in liquid while stirring, then adds water and is settled to 26ml, is uniformly mixing to obtain palladium dipping
Liquid.
Said catalyst carrier is immersed in palladium maceration extract, is aged 24 hours, obtains catalyst precarsor ii；It is in temperature
At 80 DEG C, with 8wt% aqueous sodium formate solution reducing catalyst precursor ii, recovery time 60min, the volume of aqueous sodium formate solution
For 3 times of catalyst precarsor ii volumes, catalyst precarsor iii is obtained.Catalyst precarsor iii is washed with water to cleaning solution use
AgNO3Detection is without Cl-Untill, it is dried to obtain required catalyst.By the catalyst of gained under nitrogen protection respectively 300 DEG C,
400 DEG C, the heat endurance of 500 DEG C of roastings, 8 hours investigation catalyst.
For ease of comparing, the main preparation condition of catalyst agent is listed in table 1, catalyst analysis data are listed in table 2.
【Embodiment 4】
Weigh 50 gram of 4~8 mesh, sheet cocoanut active charcoal（It is 1100m than surface2/ g, pore volume is 0.52ml/g）It is immersed in
In 3wt% aqueous sodium carbonates, the ratio between volume and activated carbon volume of aqueous sodium carbonate are 3:1, soak time is 30min, so
Drying obtains precursor carrier I afterwards；By above-mentioned precursor carrier I power output be 1000W, frequency for 2450MHz micro-wave oven in
Processing 20min obtains precursor carrier II；Then precursor carrier II is immersed in water, the volume of water is precursor carrier II volumes
3 times, be then 200W in power, then frequency is washed with water to cleaning solution in handle 30min in 40KHz ultrasonoscope
Property, obtain catalyst carrier after drying.
The preparation of palladium maceration extract：1.25 grams of 20wt% containing palladium chlorine palladium aqueous acid is weighed, it is water-soluble with 10wt% sodium carbonate
Regulation chlorine palladium aqueous acid pH to 5.5 is added dropwise in liquid while stirring, then adds water and is settled to 26ml, is uniformly mixing to obtain palladium dipping
Liquid.
Said catalyst carrier is immersed in palladium maceration extract, is aged 24 hours, obtains catalyst precarsor ii；It is in temperature
At 80 DEG C, with 8wt% aqueous sodium formate solution reducing catalyst precursor ii, recovery time 60min, the volume of aqueous sodium formate solution
For 3 times of catalyst precarsor ii volumes, catalyst precarsor iii is obtained.Catalyst precarsor iii is washed with water to cleaning solution use
AgNO3Detection is without Cl-Untill, it is dried to obtain required catalyst.By the catalyst of gained under nitrogen protection respectively 300 DEG C,
400 DEG C, the heat endurance of 500 DEG C of roastings, 8 hours investigation catalyst.
For ease of comparing, the main preparation condition of catalyst agent is listed in table 1, catalyst analysis data are listed in table 2.
【Embodiment 5】
Weigh 50 gram of 4~8 mesh, sheet cocoanut active charcoal（It is 1100m than surface2/ g, pore volume is 0.52ml/g）It is immersed in
In 3wt% aqueous sodium carbonates, the ratio between volume and activated carbon volume of aqueous sodium carbonate are 3:1, soak time is 30min, so
Drying obtains precursor carrier I afterwards；By above-mentioned precursor carrier I power output be 1000W, frequency for 2450MHz micro-wave oven in
Processing 25min obtains precursor carrier II；Then precursor carrier II is immersed in water, the volume of water is precursor carrier II volumes
3 times, be then 200W in power, then frequency is washed with water to cleaning solution in handle 30min in 40KHz ultrasonoscope
Property, obtain catalyst carrier after drying.
The preparation of palladium maceration extract：1.25 grams of 20wt% containing palladium chlorine palladium aqueous acid is weighed, it is water-soluble with 10wt% sodium carbonate
Regulation chlorine palladium aqueous acid pH to 5.5 is added dropwise in liquid while stirring, then adds water and is settled to 26ml, is uniformly mixing to obtain palladium dipping
Liquid.
Said catalyst carrier is immersed in palladium maceration extract, is aged 24 hours, obtains catalyst precarsor ii；It is in temperature
At 80 DEG C, with 8wt% aqueous sodium formate solution reducing catalyst precursor ii, recovery time 60min, the volume of aqueous sodium formate solution
For 3 times of catalyst precarsor ii volumes, catalyst precarsor iii is obtained.Catalyst precarsor iii is washed with water to cleaning solution use
AgNO3Detection is without Cl-Untill, it is dried to obtain required catalyst.By the catalyst of gained under nitrogen protection respectively 300 DEG C,
400 DEG C, the heat endurance of 500 DEG C of roastings, 8 hours investigation catalyst.
For ease of comparing, the main preparation condition of catalyst agent is listed in table 1, catalyst analysis data are listed in table 2.
【Embodiment 6】
Weigh 50 gram of 4~8 mesh, sheet cocoanut active charcoal（It is 1100m than surface2/ g, pore volume is 0.52ml/g）It is immersed in
In 3wt% aqueous sodium carbonates, the ratio between volume and activated carbon volume of aqueous sodium carbonate are 3:1, soak time is 30min, so
Drying obtains precursor carrier I afterwards；By above-mentioned precursor carrier I power output be 1000W, frequency for 2450MHz micro-wave oven in
Processing 30min obtains precursor carrier II；Then precursor carrier II is immersed in water, the volume of water is precursor carrier II volumes
3 times, be then 200W in power, then frequency is washed with water to cleaning solution in handle 30min in 40KHz ultrasonoscope
Property, obtain catalyst carrier after drying.
The preparation of palladium maceration extract：1.25 grams of 20wt% containing palladium chlorine palladium aqueous acid is weighed, it is water-soluble with 10wt% sodium carbonate
Regulation chlorine palladium aqueous acid pH to 5.5 is added dropwise in liquid while stirring, then adds water and is settled to 26ml, is uniformly mixing to obtain palladium dipping
Liquid.
Said catalyst carrier is immersed in palladium maceration extract, is aged 24 hours, obtains catalyst precarsor ii；It is in temperature
At 80 DEG C, with 8wt% aqueous sodium formate solution reducing catalyst precursor ii, recovery time 60min, the volume of aqueous sodium formate solution
For 3 times of catalyst precarsor ii volumes, catalyst precarsor iii is obtained after reduction.Catalyst precarsor iii is washed with water to cleaning solution
Use AgNO3Detection is without Cl-Untill, it is dried to obtain required catalyst.By the catalyst of gained under nitrogen protection respectively 300 DEG C,
400 DEG C, the heat endurance of 500 DEG C of roastings, 8 hours investigation catalyst.
For ease of comparing, the main preparation condition of catalyst agent is listed in table 1, catalyst analysis data are listed in table 2.
【Embodiment 7】
Weigh 50 gram of 4~8 mesh, sheet cocoanut active charcoal（It is 1100m than surface2/ g, pore volume is 0.52ml/g）It is immersed in
In 3wt% aqueous sodium carbonates, the ratio between volume and activated carbon volume of aqueous sodium carbonate are 3:1, soak time is 30min, so
Drying obtains precursor carrier I afterwards；By above-mentioned precursor carrier I power output be 1000W, frequency for 2450MHz micro-wave oven in
Processing 5min obtains precursor carrier II；Then precursor carrier II is immersed in water, the volume of water is the 3 of precursor carrier II volumes
Times, it is then 200W in power, then frequency is washed with water to cleaning solution in handle 30min in 40KHz ultrasonoscope
Property, obtain catalyst carrier after drying.
The preparation of palladium maceration extract：1.25 grams of 20wt% containing palladium chlorine palladium aqueous acid is weighed, it is water-soluble with 10wt% sodium carbonate
Regulation chlorine palladium aqueous acid pH to 4 is added dropwise in liquid while stirring, then adds water and is settled to 26ml, is uniformly mixing to obtain palladium maceration extract.
Said catalyst carrier is immersed in palladium maceration extract, is aged 24 hours, obtains catalyst precarsor ii；It is in temperature
At 80 DEG C, with 8wt% aqueous sodium formate solution reducing catalyst precursor ii, recovery time 60min, the volume of aqueous sodium formate solution
For 3 times of catalyst precarsor ii volumes, catalyst precarsor iii is obtained.Catalyst precarsor iii is washed with water to cleaning solution use
AgNO3Detection is without Cl-Untill, it is dried to obtain required catalyst.By the catalyst of gained under nitrogen protection respectively 300 DEG C,
400 DEG C, the heat endurance of 500 DEG C of roastings, 8 hours investigation catalyst.
For ease of comparing, the main preparation condition of catalyst agent is listed in table 1, catalyst analysis data are listed in table 2.
【Embodiment 8】
Weigh 50 gram of 4~8 mesh, sheet cocoanut active charcoal（It is 1100m than surface2/ g, pore volume is 0.52ml/g）It is immersed in
In 3wt% aqueous sodium carbonates, the ratio between volume and activated carbon volume of aqueous sodium carbonate are 3:1, soak time is 30min, so
Drying obtains precursor carrier I afterwards；By above-mentioned precursor carrier I power output be 1000W, frequency for 2450MHz micro-wave oven in
Processing 5min obtains precursor carrier II；Then precursor carrier II is immersed in water, the volume of water is the 3 of precursor carrier II volumes
Times, it is then 200W in power, then frequency is washed with water to cleaning solution in handle 30min in 40KHz ultrasonoscope
Property, obtain catalyst carrier after drying.
The preparation of palladium maceration extract：1.25 grams of 20wt% containing palladium chlorine palladium aqueous acid is weighed, it is water-soluble with 10wt% sodium carbonate
Regulation chlorine palladium aqueous acid pH to 5 is added dropwise in liquid while stirring, then adds water and is settled to 26ml, is uniformly mixing to obtain palladium maceration extract.
Said catalyst carrier is immersed in palladium maceration extract, is aged 24 hours, obtains catalyst precarsor ii；It is in temperature
At 80 DEG C, with 8wt% aqueous sodium formate solution reducing catalyst precursor ii, recovery time 60min, the volume of aqueous sodium formate solution
For 3 times of catalyst precarsor ii volumes, catalyst precarsor iii is obtained.Catalyst precarsor iii is washed with water to cleaning solution use
AgNO3Detection is without Cl-Untill, it is dried to obtain required catalyst.By the catalyst of gained under nitrogen protection respectively 300 DEG C,
400 DEG C, the heat endurance of 500 DEG C of roastings, 8 hours investigation catalyst.
For ease of comparing, the main preparation condition of catalyst agent is listed in table 1, catalyst analysis data are listed in table 2.
【Embodiment 9】
Weigh 50 gram of 4~8 mesh, sheet cocoanut active charcoal（It is 1100m than surface2/ g, pore volume is 0.52ml/g）It is immersed in
In 3wt% aqueous sodium carbonates, the ratio between volume and activated carbon volume of aqueous sodium carbonate are 3:1, soak time is 30min, so
Drying obtains precursor carrier I afterwards；By above-mentioned precursor carrier I power output be 1000W, frequency for 2450MHz micro-wave oven in
Processing 5min obtains precursor carrier II；Then precursor carrier II is immersed in water, the volume of water is the 3 of precursor carrier II volumes
Times, it is then 200W in power, then frequency is washed with water to cleaning solution in handle 30min in 40KHz ultrasonoscope
Property, obtain catalyst carrier after drying.
The preparation of palladium maceration extract：1.25 grams of 20wt% containing palladium chlorine palladium aqueous acid is weighed, it is water-soluble with 10wt% sodium carbonate
Regulation chlorine palladium aqueous acid pH to 6.0 is added dropwise in liquid while stirring, then adds water and is settled to 26ml, is uniformly mixing to obtain palladium dipping
Liquid.
Said catalyst carrier is immersed in palladium maceration extract, is aged 24 hours, obtains catalyst precarsor ii；It is in temperature
At 80 DEG C, with 8wt% aqueous sodium formate solution reducing catalyst precursor ii, recovery time 60min, the volume of aqueous sodium formate solution
For 3 times of catalyst precarsor ii volumes, catalyst precarsor iii is obtained.Catalyst precarsor iii is washed with water to cleaning solution use
AgNO3Detection is without Cl-Untill, it is dried to obtain required catalyst.By the catalyst of gained under nitrogen protection respectively 300 DEG C,
400 DEG C, the heat endurance of 500 DEG C of roastings, 8 hours investigation catalyst.
For for ease of comparing, the main preparation condition of catalyst agent is listed in into table 1, catalyst analysis data are listed in table 2.
【Embodiment 10】
Weigh 50 gram of 4~8 mesh, sheet cocoanut active charcoal（It is 1100m than surface2/ g, pore volume is 0.52ml/g）It is immersed in
In 3wt% aqueous sodium carbonates, the ratio between volume and activated carbon volume of aqueous sodium carbonate are 3:1, soak time is 30min, so
Drying obtains precursor carrier I afterwards；By above-mentioned precursor carrier I power output be 1000W, frequency for 2450MHz micro-wave oven in
Processing 5min obtains precursor carrier II；Then precursor carrier II is immersed in water, the volume of water is the 3 of precursor carrier II volumes
Times, it is then 200W in power, then frequency is washed with water to cleaning solution in handle 30min in 40KHz ultrasonoscope
Property, obtain catalyst carrier after drying.
The preparation of palladium maceration extract：1.25 grams of 20wt% containing palladium chlorine palladium aqueous acid is weighed, it is water-soluble with 10wt% sodium carbonate
Regulation chlorine palladium aqueous acid pH to 6.5 is added dropwise in liquid while stirring, then adds water and is settled to 26ml, is uniformly mixing to obtain palladium dipping
Liquid.
Said catalyst carrier is immersed in palladium maceration extract, is aged 24 hours, obtains catalyst precarsor ii；It is in temperature
At 80 DEG C, with 8wt% aqueous sodium formate solution reducing catalyst precursor ii, recovery time 60min, the volume of aqueous sodium formate solution
For 3 times of catalyst precarsor ii volumes, catalyst precarsor iii is obtained.Catalyst precarsor iii is washed with water to cleaning solution use
AgNO3Detection is without Cl-Untill, it is dried to obtain required catalyst.By the catalyst of gained under nitrogen protection respectively 300 DEG C,
400 DEG C, the heat endurance of 500 DEG C of roastings, 8 hours investigation catalyst.
For ease of comparing, the main preparation condition of catalyst agent is listed in table 1, catalyst analysis data are listed in table 2.
【Embodiment 11】
Weigh 50 gram of 4~8 mesh, sheet cocoanut active charcoal（It is 1100m than surface2/ g, pore volume is 0.52ml/g）It is immersed in
In 3wt% aqueous sodium carbonates, the ratio between volume and activated carbon volume of aqueous sodium carbonate are 3:1, soak time is 30min, so
Drying obtains precursor carrier I afterwards；By above-mentioned precursor carrier I power output be 1000W, frequency for 2450MHz micro-wave oven in
Processing 5min obtains precursor carrier II；Then precursor carrier II is immersed in water, the volume of water is the 3 of precursor carrier II volumes
Times, it is then 200W in power, then frequency is washed with water to cleaning solution in handle 30min in 40KHz ultrasonoscope
Property, obtain catalyst carrier after drying.
The preparation of palladium maceration extract：1.25 grams of 20wt% containing palladium chlorine palladium aqueous acid is weighed, it is water-soluble with 10wt% sodium carbonate
Regulation chlorine palladium aqueous acid pH to 7.0 is added dropwise in liquid while stirring, then adds water and is settled to 26ml, is uniformly mixing to obtain palladium dipping
Liquid.
Said catalyst carrier is immersed in palladium maceration extract, is aged 24 hours, obtains catalyst precarsor ii；It is in temperature
At 80 DEG C, with 8wt% aqueous sodium formate solution reducing catalyst precursor ii, recovery time 60min, the volume of aqueous sodium formate solution
For 3 times of catalyst precarsor ii volumes, catalyst precarsor iii is obtained.Catalyst precarsor iii is washed with water to cleaning solution use
AgNO3Detection is without Cl-Untill, it is dried to obtain required catalyst.By the catalyst of gained under nitrogen protection respectively 300 DEG C,
400 DEG C, the heat endurance of 500 DEG C of roastings, 8 hours investigation catalyst.
For ease of comparing, the main preparation condition of catalyst agent is listed in table 1, catalyst analysis data are listed in table 2.
【Comparative example 1】
Weigh 50 gram of 4~8 mesh, sheet cocoanut active charcoal（It is 1100m than surface2/ g, pore volume is 0.52ml/g）In output
Power is 1000W, and frequency is handles 5min in 2450MHz micro-wave oven；Then the activated carbon after microwave treatment is immersed in water
In, the volume of water is 3 times of activated carbon volume, is then 200W in power, frequency is processing in 40KHz ultrasonoscope
30min, is then washed with water to cleaning solution into neutrality, catalyst carrier is obtained after drying.
The preparation of palladium maceration extract：1.25 grams of 20wt% containing palladium chlorine palladium aqueous acid is weighed, it is water-soluble with 10wt% sodium carbonate
Regulation chlorine palladium aqueous acid pH to 5.5 is added dropwise in liquid while stirring, then adds water and is settled to 26ml, is uniformly mixing to obtain palladium dipping
Liquid.
Said catalyst carrier is immersed in palladium maceration extract, is aged 24 hours, obtains catalyst precarsor ii；It is in temperature
At 80 DEG C, with 8wt% aqueous sodium formate solution reducing catalyst precursor ii, recovery time 60min, the volume of aqueous sodium formate solution
For 3 times of catalyst precarsor ii volumes, catalyst precarsor iii is obtained after reduction.Catalyst precarsor iii is washed with water to cleaning solution
Use AgNO3Detection is without Cl-Untill, it is dried to obtain required catalyst.By the catalyst of gained under nitrogen protection respectively 300 DEG C,
400 DEG C, the heat endurance of 500 DEG C of roastings, 8 hours investigation catalyst.
For ease of comparing, the main preparation condition of catalyst agent is listed in table 1, catalyst analysis data are listed in table 2.
【Comparative example 2】
Weigh 50 gram of 4~8 mesh, sheet cocoanut active charcoal（It is 1100m than surface2/ g, pore volume is 0.52ml/g）, water cleaning
The powder falling of activated carbon surface is removed, catalyst carrier is obtained after drying.
The preparation of palladium maceration extract：1.25 grams of 20wt% containing palladium chlorine palladium aqueous acid is weighed, then adds water and is settled to 26ml,
It is uniformly mixing to obtain palladium maceration extract.
Said catalyst carrier is immersed in palladium maceration extract, is aged 24 hours, obtains catalyst precarsor ii；It is in temperature
At 80 DEG C, with 8wt% aqueous sodium formate solution reducing catalyst precursor ii, recovery time 60min, the volume of aqueous sodium formate solution
For 3 times of catalyst precarsor ii volumes, catalyst precarsor iii is obtained after reduction.Catalyst precarsor iii is washed with water to cleaning solution
Use AgNO3Detection is without Cl-Untill, it is dried to obtain required catalyst.By the catalyst of gained under nitrogen protection respectively 300 DEG C,
400 DEG C, the heat endurance of 500 DEG C of roastings, 8 hours investigation catalyst.
For ease of comparing, the main preparation condition of catalyst agent is listed in table 1, catalyst analysis data are listed in table 2.
【Comparative example 3】
Weigh 50 gram of 4~8 mesh, sheet cocoanut active charcoal（It is 1100m than surface2/ g, pore volume is 0.52ml/g）, water cleaning
The powder falling of activated carbon surface is removed, catalyst carrier is obtained after drying.
The preparation of palladium maceration extract：1.25 grams of 20wt% containing palladium chlorine palladium aqueous acid is weighed, it is water-soluble with 10wt% sodium carbonate
Regulation chlorine palladium aqueous acid pH to 5.5 is added dropwise in liquid while stirring, then adds water and is settled to 26ml, is uniformly mixing to obtain palladium dipping
Liquid.
Said catalyst carrier is immersed in palladium maceration extract, is aged 24 hours, obtains catalyst precarsor ii；It is in temperature
At 80 DEG C, with 8wt% aqueous sodium formate solution reducing catalyst precursor ii, recovery time 60min, the volume of aqueous sodium formate solution
For 3 times of catalyst precarsor ii volumes, catalyst precarsor iii is obtained after reduction.Catalyst precarsor iii is washed with water to cleaning solution
Use AgNO3Detection is without Cl-Untill, it is dried to obtain required catalyst.By the catalyst of gained under nitrogen protection respectively 300 DEG C,
400 DEG C, the heat endurance of 500 DEG C of roastings, 8 hours investigation catalyst.
For ease of comparing, the main preparation condition of catalyst agent is listed in table 1, catalyst analysis data are listed in table 2.
【Comparative example 4】
Take the BASF of commercialization CBA-300 hydrofining crude terephthalic acid palladium carbon catalysts, under nitrogen protection 300
DEG C, 400 DEG C, 500 DEG C be calcined and investigate within 8 hours the heat endurance of the catalyst.
For ease of comparing, the main preparation condition of catalyst agent is listed in table 1, catalyst analysis data are listed in table 2.
Table 1.
Table 2.
Claims (9)
1. the preparation method of hydrofining crude terephthalic acid catalyst, the catalyst includes carrier and active component, described
Active component is palladium, and the weight/mass percentage composition of palladium is the 0.2~1.0% of catalyst dry weight, it is characterized in that the carrier is through micro-
Activated carbon after ripple processing and ultrasonication, comprises the following steps：
(1) activated carbon is mixed with alkaline compound solution, then drying obtains precursor carrier I；
(2) to precursor carrier I microwave treatments, precursor carrier II is obtained；
(3) precursor carrier II is immersed in water through ultrasonication, be then washed to cleaning solution into it is neutral, be dried to obtain catalyst
Carrier；
(4) pH value for adjusting the containing palladium compound aqueous solution by alkali compounds obtains palladium maceration extract to 1~10；
(5) catalyst carrier is mixed with palladium maceration extract, obtains catalyst precarsor i；
(6) it is aged, obtains catalyst precarsor ii；
(7) compound state palladium is reduced to simple substance palladium with reducing agent, obtains catalyst precarsor iii；
(8) washing removes the impurity in catalyst precarsor iii, obtains described catalyst.
2. preparation method according to claim 1, it is characterised in that described activated carbon is selected from ature of coal charcoal, carbo lignius or fruit
At least one of shell charcoal.
3. preparation method according to claim 2, it is characterised in that described fruit shell carbon is coconut husk charcoal.
4. preparation method according to claim 3, it is characterised in that described coconut husk charcoal is 800~1600m than surface2/ g,
Pore volume is 0.35~0.80ml/g.
5. preparation method according to claim 1, it is characterized in that step (1) described alkali compounds is selected from alkali metal hydrogen-oxygen
At least one of compound, alkali carbonate or ammonia.
6. preparation method according to claim 1, it is characterized in that step (2) described microwave output power be 600~
2000W, frequency is 2450MHz, 1~60min of processing time.
7. preparation method according to claim 1, it is characterized in that step (3) ultrasonic power output 100~
2000W, 1~60min of processing time.
8. preparation method according to claim 1, it is characterised in that described containing palladium compound is selected from palladium nitrate, acetic acid
Palladium, chlorine palladium acid and its at least one of salt and the ammino palladium of dichloro four.
9. preparation method according to claim 1, it is characterised in that step (4) described alkali compounds is alkali metal hydrogen-oxygen
At least one of compound, alkali carbonate or ammoniacal liquor.
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