CN106492818B - A kind of heterogeneous catalysis and preparation method thereof, and the method using the catalyst preparation 3,5-dimethylphenol - Google Patents
A kind of heterogeneous catalysis and preparation method thereof, and the method using the catalyst preparation 3,5-dimethylphenol Download PDFInfo
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Abstract
The present invention relates to a kind of heterogeneous catalysis and preparation method thereof, the method using the heterogeneous catalysis by isophorone (IP) aromatisation preparation 3,5-dimethylphenol is further related to.The heterogeneous catalysis includes active component, carrier and optional auxiliary agent, and the active component includes Ni, NiO, Cr2O3And Co3O4.The heterogeneous catalysis of activation is used for isophorone aromatization, is provided simultaneously with aromatization activity and methane CO2Reforming reaction activity, the heterogeneous catalysis activity is good, selectivity is high, stability is good, and use is cooperateed with homogeneous catalyst, can effectively reduce the usage amount of homogeneous catalyst, while can reduce carbon deposition quantity, and extend catalyst uses the time.
Description
Technical field
The invention belongs to catalyst fields, and in particular to a kind of catalyst by isophorone preparation 3,5-dimethylphenol
And preparation method thereof, the method for further relating to preparation 3,5-dimethylphenol.
Background technique
3,5-dimethylphenol is a kind of important organic synthesis intermediate and fine chemical material, is widely used in dimension life
The production of element, disinfectant, rubber, dyestuff, coating etc..Domestic most important purposes is to generate 3,5-dimethylphenol chlorination
4-chloro-3,5-dimethylphenol (PCMX), this is a kind of high effect disinfectants and preservative, for the washing such as perfumed soap and hand cleanser
Agent.Under the catalysis of noble metal catalyst, being passed through hydrogen and ammonia reaction can synthesize in high-grade dyestuff 3,5-dimethylphenol
Mesosome 3,5- dimethylaniline；3,5-dimethylphenol is alkylated with methanol and is reacted, 2,3,5- trimethylbenzenes can be produced
Phenol, the raw material as preparation medicine.It is reacted with dimethyl disulfide with 3,5-dimethylphenol, produces 3,5- dimethyl -4- first
Sulfenyl phenol, it is to prepare carbamate insecticides to go out the intermediate of rib prestige.In addition, 3,5-dimethylphenol can be used for rolling
Steel cold rolling oil additive, the high-quality resistance to nontoxic turbine oil additive of combustion, can extend the service life of rolling mill cold-rolled lubricating oil and turbine oil；In recent years
Come, also shows that wide application prospect at the antimicrobial DP finish research aspect of synthesizing efficient, wide spectrum.
Traditional 3,5-dimethylphenol, is mainly derived from coal tar, but its quantity be it is extremely limited, can not expire at all
The industrial needs of foot.Wanted simultaneously by 3,5- xylenol is isolated in complicated coal tar oil ingredient to be also quite tired
Difficult.
Currently, the production method of 3,5-dimethylphenol mainly has: alkylation of phenol, meta-xylene sulfonated alkali fusion method, 3,
5- dimethyl -2- cyclonene dehydriding, isophorone aromatisation method.The problem of first three methods are primarily present at present has: producing
Object is selectively low and by-product is low；Strong acid and/or highly basic, equipment seriously corroded, complex technical process are used in the process, it is difficult to
Obtain the higher product of purity.And isophorone (IP) aromatisation preparation 3,5-dimethylphenol atom utilization is high, have compared with
High yield.
IP aromatisation early stage mainly uses CH3I is catalyst, and advantage is that activity is high, and selectivity is good, such as US4086282 and
It all reports in two patents of CN101348421 using halogenated hydrocarbons such as iodomethane, n-butyl bromide, carbon tetrachloride as homogeneous catalysis
Agent, but since the reaction is carried out at 500-600 DEG C of high temperature, catalyst is easily inactivated because of carbon distribution, coking, usually using the longevity
Life is no more than 50h.And the catalyst is expensive, is not suitable for industrial application；Later, people developed a kind of Cr2O3/
Al2O3Catalyst, the catalyst overcome the deficiency that aforementioned catalytic agent is easy carbon distribution, coking, and disadvantage is that conversion ratio is unstable,
Inactivation is very fast.The patents such as US4086282, GB1197803, GB1181437, US44453025, US4533769, DE2529773 text
It offers and has reported Al2O3、Cr2O3、Cu2O、MgO、MnO、K2A kind of metal oxide of O etc. or several metal composite oxide conducts
Catalyst can obtain higher conversion ratio, and simple process, and catalyst is easy preparation, cheap, but in reaction process
It is easy inactivation, selectivity is also undesirable.Therefore, it for the reaction, develops a kind of efficient, low in cost and maneuverable
Catalyst has important Practical significance.
When carrying out isophorone aromatization, more carbon distribution is often generated in reactor, methane is as isophorone
The Main By product of aromatisation, under the conditions of existing for the aromatisation metallic catalyst such as Mg, Co, Mo, it is easy to generate carbon distribution.
Technical problem of the existing technology:
(1) catalyst mostly uses single type catalyst, and single phase catalysis agent results in catalysis effect because of the limitation of its own
The decline of fruit；
(2) carbon distribution is serious during the reaction, and the carbon dust generated in reaction process will by the accumulation meeting of long period
Reactor plugs cause the passive parking of entire reaction system；
(3) active component Cr will lead to environmental pollution, and therefore, effective fixation of active component is the pass for solving environmental pollution
Key.
Summary of the invention
The object of the present invention is to provide a kind of isophorone (IP) prepare 3,5- xylenol heterogeneous catalysis and
Preparation method.The heterogeneous catalysis activity is good, selectivity is high, stability is good, reaction process is easy to control, with homogeneous catalysis
Agent collaboration uses, and can effectively reduce the usage amount of homogeneous catalyst, while can reduce carbon deposition quantity, and can guarantee non-equal
Phase catalyst higher selectivity, while IP is further converted, improve the conversion ratio of raw material.
To achieve the above object, the technical solution adopted by the present invention is that:
A kind of heterogeneous catalysis of IP aromatisation preparation 3,5-dimethylphenol includes active component, carrier and optionally
Auxiliary agent, the active component includes Ni, NiO, Cr2O3And Co3O4。
In heterogeneous catalysis of the present invention, the Ni is Ni simple substance.
In heterogeneous catalysis of the present invention, the Ni content is 5-20wt%, preferably 6-15wt%, with non-equal
The total weight of phase catalyst calculates；The content of NiO is 5-20wt%, preferably 7-15wt%, with the total weight of heterogeneous catalysis
It calculates.
In heterogeneous catalysis of the present invention, the mass ratio of the Ni and NiO are 2:3-3:1, preferably 3:4-3:
2。
Simple substance content is relatively low in heterogeneous catalysis will lead to catalyst performance deficiency, and carbon distribution still can occur, and higher
Ni content then will affect the performance of catalyst IP aromatisation.
Cr of the present invention2O3And Co3O4Content be 15-50wt%, preferably 35-45wt%, with heterogeneous catalysis
It is calculated on the basis of agent gross mass.
Cr of the present invention2O3With Co3O4Mass ratio be 3:5-9:1, preferably 6:1-8:1.
Auxiliary agent of the present invention is selected from one or both of alkali and alkaline earth metal ions oxide or a variety of, preferably
One or both of CaO and MgO.
The content of auxiliary agent of the present invention is 0-20wt%, preferably 5-10wt%, using heterogeneous catalysis gross mass as base
Standard calculates.
The content of carrier of the present invention is 30-70wt%, preferably 35-45wt%, is with heterogeneous catalysis gross mass
Benchmark.
Carrier of the present invention is selected from SiO2、Al2O3、ZrO2, molecular sieve and TiO2One or both of or it is a variety of, it is excellent
Select γ-Al2O3And inertia Al2O3Mixture, more preferable inertia Al2O3Account for γ-Al2O3And inertia Al2O3The 20- of total weight
50wt%.Two kinds of Al2O3It is used in mixed way the binding force that can enhance catalyst, improves the strength of pressed pieces of catalyst, weakens catalyst
Part in forming process.
The present invention also provides a kind of preparation methods of heterogeneous catalysis, comprising the following steps:
(1) water is added into reaction kettle, expanding agent and Ni powder is then added, is heated to 40-120 DEG C, preferably 60-90 DEG C；
(2) proportionally, chromic salts, cobalt salt, nickel salt, the salt of auxiliary agent, aluminium salt are dissolved in distilled water, obtained concentration is
Mixed-salt aqueous solution is added in reaction kettle with alkaline precipitating agent cocurrent and precipitates by the mixed-salt aqueous solution of 0.5-2mol/L,
Inertia Al2O3It is added portionwise in precipitation system, controls 60-90 DEG C of precipitation process temperature, pH 5.0-8.0, sedimentation time 1-
System pH with alkaline precipitating agent is adjusted to 7.0-9.0 after adding, then obtained in 60~90 DEG C of aging 1-3h by 3h, mixing salt solution
Slurry；
(3) slurry is washed through filtering, then using water, is roasted in 80-120 DEG C of dry 8-16h, and in 600-900 DEG C
Burn 2-8h.
Chromic salts of the present invention preferably is selected from Cr (NO3)3.9H2O、(CH3COO)3Cr and Cr2(SO4)3One or both of
Or it is a variety of.
Cobalt salt of the present invention preferably is selected from Co (NO3)2.6H2O、(CH3COO)2Co.4H2O、CoSO4.7H2O and CoCO3In
It is one or two or more kinds of.
Nickel salt of the present invention preferably is selected from Ni (NO3)2.6H2O、(CH3COO)2Ni、NiSO4.6H2O and NiCO3One of
Or two or more.
Aluminium salt of the present invention preferably is selected from Al (NO3)3.9H2O、(C3H7O)3Al and NaAlO2One or both of or it is more
Kind.
The salt of auxiliary agent of the present invention is selected from one or both of alkali metal salt and alkali salt or a variety of.
Alkali metal salt of the present invention preferably is selected from water-soluble alkali metal salt.
Alkali salt of the present invention preferably is selected from water-soluble alkali salt, more preferable Mg (NO3)2.6H2O and/
Or Ca (NO3)2.4H2O。
Alkaline precipitating agent of the present invention be selected from one or both of sodium carbonate, ammonium nitrate, ammonium hydroxide and sodium hydroxide or
It is a variety of, preferred sodium carbonate.
Expanding agent of the present invention is selected from one of polyethylene glycol, polyvinyl alcohol, ceramic fibre, paraffin and wood fibre
Or two or more, dosage 0.2-3wt%, preferably 1.5-2.5wt% are calculated on the basis of heterogeneous catalysis gross mass.
Expanding agent is capable of increasing catalyst pore-size distribution, is conducive to the diffusion of reactant and product, reduces the influence of carbon distribution.
Heterogeneous catalysis of the present invention needs to carry out before use reduction activation, and reduction temperature is 330-380 DEG C,
It is preferred that 340-360 DEG C；H2Air speed is 10-1000h-1, keep 1-5h.It needs NiO and Co simultaneously3O4Be reduced to simple substance Ni and
CoO.Therefore the selection of reduction temperature is more important.Co3O4The reduction temperature for being reduced into CoO is 230~330 DEG C, and CoO is restored
Reduction temperature at simple substance Co is respectively 330-450 DEG C, under reduction temperature of the invention, Co3O4It is reduced to CoO completely,
And CoO only have it is minimal amount of by over reduction be Co, the CoO that this part is reduced on it is active influence it is less, can ignore；
The reduction temperature that NiO is reduced to simple substance Ni is 300-450 DEG C, and under reduction temperature of the invention, part NiO is reduced to Ni, separately
A part still maintains the state of NiO, and NiO is poor to methane reforming activity.In order to improve the activity of methane reforming, need to guarantee
Content of the Ni in the heterogeneous catalysis after reduction activation, therefore under reduction temperature of the invention, how in reduction activation
Higher simple substance Ni content is kept to become the key for determining methane reforming reaction performance in heterogeneous catalysis afterwards.
The present invention is introduced into W metal powder as a kind of source Ni in heterogeneous catalysis, to improve methane reforming catalytic
Energy.NiO from nickel salt decomposition can be good at being dispersed on carrier, and the addition of Ni powder needs not move through reduction and can rise
To catalytic effect, the content of active component Ni simple substance in the heterogeneous catalysis after capable of effectively improving reduction activation, simultaneously
Introducing Ni powder can be improved the intensity after shaped catalyst.If Ni element, completely using Ni powder as source, Ni can be because of Ni powder and load
Binding force is insufficient and be lost between body, leads to active decline in reaction process, while occurring Ni powder in product and will cause separation
Difficulty.And the source Ni of two kinds of forms of nickel powder and nickel salt is used simultaneously, respective advantage and interaction can be solved effectively
Certainly above-mentioned problem.
The present invention also provides the methods of IP aromatisation preparation 3,5-dimethylphenol comprising the steps of: in inert gas
And CO2In atmosphere, isophorone is reacted under the catalysis of the heterogeneous catalysis and homogeneous catalyst of activation, will preferably be contained
There is the mixed solution of homogeneous catalyst and isophorone to import in the reactor of the heterogeneous catalysis equipped with activation to react, react
Temperature is 350-700 DEG C, reaction pressure 0-2MPa.
Homogeneous catalyst of the present invention is selected from halogenated alkane, preferably is selected from CH3I、CH2I2One or both of with HI
Or it is a variety of, homogeneous catalysis agent content is 0.01-5wt%, preferably 0.1-2wt%, more preferably 0.5-1wt%, with different Fo Er
The quality meter of ketone.
Volume ratio 100:1-1000:1, the preferably 500:1-800:1 of inert gas of the present invention and isophorone charging,
The preferred nitrogen of the inert gas.
CO of the present invention2Volume fraction be 0.05-2%, preferably 0.5-1%, calculated with the volume of inert gas,
CO2Raw material as methane reforming reaction.
Also contain coking inhibitor, the inhibition in the mixed solution of homogeneous catalyst and isophorone of the present invention
Agent is selected from one or both of methanol, water, hexamethylene, cyclohexanol and naphthane or a variety of, the dosage of the coking inhibitor
For 0.5-5wt%, preferably 1-3wt%, calculated on the basis of the quality of isophorone.
Volume liquid hourly space velocity (LHSV) (LHSV)=0.1-2h of liquid feedstock of the present invention-1, preferably 0.5-1.5h-1。
Pressure of the present invention is absolute pressure.
" optional " meaning of the present invention is " containing " or " being free of ".
Of the invention has the advantages that
(1) catalytic activity is high when heterogeneous catalysis is for isophorone preparation 3,5-dimethylphenol reaction, product choosing
Selecting property is good, and intensity is high, and the service life is long；
(2) byproduct methane can be restructured as synthesis gas by heterogeneous catalysis, to inhibit the generation of carbon distribution；
(3) heterogeneous catalysis preparation process is simple, and active component dispersion degree is high, has between active component and carrier suitable
Suitable interaction, and then catalyst has the characteristics that intensity is high, stability is good.
(4) heterogeneous catalysis cooperates with use with homogeneous catalyst, both ensure that the high conversion ratio of homogeneous catalyst and non-
The high selectivity of homogeneous catalyst, while the defect of easy carbon distribution is overcome again, improve the service life of catalyst.
(5) IP conversion ratio is 95-100% in heterogeneous catalysis, and 3,5-dimethylphenol is selectively 90-95%, CO2
The conversion ratio of methane reforming reaction is 90-95%, which has high catalytic performance.
Specific embodiment
The method of the present invention is described in detail below with reference to embodiment, but is not limited to the embodiment.
Embodiment 1
Catalyst is prepared using the precipitation method, 2kg water, 2.6g polyethylene glycol and 15.6gNi powder are added in kettle, is heated to 70
℃.By 273.7g Cr (NO3)3.9H2O、23.57g Co(NO3)2.6H2O、40.47g Ni(NO3)2.6H2O and 200.8g Al
(NO3)3.9H2The O mixing salt solution soluble in water for being configured to 1.5mol/L.By mixing salt solution and the sodium carbonate liquor of 15wt%
It instills in reaction kettle simultaneously, titration time 1h, it is 70 DEG C that reaction temperature is kept in titration process, and divides 4 in precipitation process
Secondary addition 18.2g inertia Al2O3, system pH control is 6.5.After salting liquid to be mixed adds, using sodium carbonate liquor by system pH
It is adjusted to 7.5, and the aging 3h at 70 DEG C, is then filtered, washed and by filter cake in 110 DEG C of dry 12h, and in 600 DEG C of roasting 3h.
Obtain 1# heterogeneous catalysis 40Cr2O3/8NiO/12Ni/5Co3O4/35Al2O3, heterogeneous catalysis composition in numerical value be corresponding
The mass parts of substance.
Forming and activation: using the fixed bed reactors of Φ 15mm, 1# heterogeneous catalysis tabletting is catalyzed at 5*5mm
Agent is packed into reactor, loadings 10mL, N of the catalyst at 150 DEG C after being broken for 16-30 mesh2Under the conditions of keep 1h, then
It is switched to air speed 300h-1H2In 350 DEG C of reduction 4h.
Activity rating: containing isophorone, homogeneous catalyst and coking inhibitor in liquid phase feeding, homogeneous catalyst uses
CH3I, dosage are the 0.5% of isophorone quality, and coking inhibitor accounts for the 2% of isophorone quality, and coking inhibitor is by matter
Amount is constituted than the mixture of the water, methanol, hexamethylene and the naphthane that are 5:3:1:1.The charging rate 10ml/h of liquid phase feeding, body
Product liquid hourly space velocity (LHSV) is LHSV=1h-1.Reaction temperature is 600 DEG C, reaction pressure 0.2MPa, N2Charge flow rate is 100ml/min,
One accounts for N2The CO of volume fraction 1%2As the unstripped gas of methane reforming reaction, gas and liquid feedstock are led to by reactor head
Enter reactor, product is flowed out by bottom, and collects 3,5-dimethylphenol by condensing unit.Reaction carries out 300h, reaction knot
Fruit and catalyst carbon deposition situation are shown in Table 1.
Embodiment 2
Catalyst is prepared using the precipitation method, 2kg water, 2.6g polyethylene glycol and 11.7gNi powder are added in kettle, is heated to 70
℃.By 239.5g Cr (NO3)3.9H2O、23.57g Co(NO3)2.6H2O、45.5g Ni(NO3)2.6H2O、41.36g Mg
(NO3)2.6H2O and 247.7g Al (NO3)3.9H2The O mixing salt solution soluble in water for being configured to 1mol/L.By mixing salt solution
And the sodium carbonate liquor of 15wt% instills in reaction kettle simultaneously, titration time 2h, it is 70 that reaction temperature is kept in titration process
DEG C, and point 4 addition 14.4g inertia Al in precipitation process2O3, system pH control is 6.0.After salting liquid to be mixed adds, adopt
System pH is adjusted to 7.0, and the aging 3h at 70 DEG C with sodium carbonate liquor, is then filtered, washed and by filter cake in 110 DEG C of dryings
12h, and in 700 DEG C of roasting 3h.Obtain 2# heterogeneous catalysis 35Cr2O3/9NiO/9Ni/5MgO/5Co3O4/37Al2O3, heterogeneous
Numerical value in catalyst composition is the mass parts of respective substance.
Forming and activation: using the fixed bed reactors of Φ 15mm, 2# heterogeneous catalysis tabletting is catalyzed at 5*5mm
Agent is packed into reactor, loadings 10mL, N of the catalyst at 150 DEG C after being broken for 16-30 mesh2Under the conditions of keep 1h, then
It is switched to 500h-1H2In 340 DEG C of reduction 4h.
Activity rating: activity rating method same as Example 1 is used.Reaction carries out 300h, reaction result and catalysis
Agent carbon distribution situation is shown in Table 1.
Embodiment 3
Catalyst is prepared using the precipitation method, 2kg water, 2.0g polyethylene glycol and 7.8gNi powder are added in kettle, is heated to 75
DEG C, by 205.28g Cr (NO3)3.9H2O、70.71g Co(NO3)2.6H2O、45.5g Ni(NO3)2.6H2O and 229.49g Al
(NO3)3.9H2The O mixing salt solution soluble in water for being configured to 1.5mol/L.By mixing salt solution and the sodium carbonate liquor of 15wt%
It instills in reaction kettle simultaneously, titration time 1.5h, it is 75 DEG C that reaction temperature is kept in titration process, and is divided in precipitation process
4 addition 20.8g inertia Al2O3, system pH control is 7.0.After salting liquid to be mixed adds, using sodium carbonate liquor by system
PH is adjusted to 8.0, and the aging 3h at 75 DEG C, is then filtered, washed and by filter cake in 110 DEG C of dry 12h, and roasts in 650 DEG C
3h.Obtain 3# heterogeneous catalysis 30Cr2O3/9NiO/6Ni/15Co3O4/40Al2O3, heterogeneous catalysis composition in numerical value be
The mass parts of respective substance.
Forming and activation: using the fixed bed reactors of Φ 15mm, 3# heterogeneous catalysis tabletting is catalyzed at 5*5mm
Agent is packed into reactor, loadings 10mL, N of the catalyst at 150 DEG C after being broken for 16-30 mesh2Under the conditions of keep 1h, then
It is switched to 300h-1H2In 360 DEG C of reduction 4h.
Activity rating: activity rating method same as Example 1 is used.Reaction carries out 300h, reaction result and catalysis
Agent carbon distribution situation is shown in Table 1.
Embodiment 4
Catalyst is prepared using the precipitation method, 2kg water, 2.6g polyethylene glycol and 7.8gNi powder are added in kettle, is heated to 80
DEG C, by 239.49g Cr (NO3)3.9H2O、23.57g Co(NO3)2.6H2O、45.5g Ni(NO3)2.6H2O、27.37g Ca
(NO3)2.4H2O and 229.49g Al (NO3)3.9H2The O mixing salt solution soluble in water for being configured to 2mol/L.By mixing salt solution
And the sodium carbonate liquor of 15wt% instills in reaction kettle simultaneously, titration time 3h, it is 80 that reaction temperature is kept in titration process
DEG C, and point 4 addition 20.8g inertia Al in precipitation process2O3, system pH control is 7.5.After salting liquid adds, using carbon
System pH is adjusted to 8.5, and the aging 3h at 80 DEG C by acid sodium solution, is then filtered, washed and by filter cake in 110 DEG C of dry 12h,
And in 800 DEG C of roasting 3h.Obtain 4# heterogeneous catalysis 35Cr2O3/9NiO/6Ni/5CaO/5Co3O4/40Al2O3, heterogeneous catalysis
Numerical value in agent composition is the mass parts of respective substance.
Forming and activation: using the fixed bed reactors of Φ 15mm, 4# heterogeneous catalysis tabletting is catalyzed at 5*5mm
Agent is packed into reactor, loadings 10mL, N of the catalyst at 150 DEG C after being broken for 16-30 mesh2Under the conditions of keep 1h, then
It is switched to 1000h-1H2In 340 DEG C of reduction 4h.
Activity rating: activity rating method same as Example 1 is used.Reaction carries out 300h, reaction result and catalysis
Agent carbon distribution situation is shown in Table 1.
Embodiment 5
Catalyst is prepared using the precipitation method, 2kg water, 2.6g polyethylene glycol and 14gNi powder are added in kettle, is heated to 70
℃.By 273.7g Cr (NO3)3.9H2O、23.57g Co(NO3)2.6H2O、36.4g Ni(NO3)2.6H2O and 247.7g Al
(NO3)3.9H2The O mixing salt solution soluble in water for being configured to 1.5mol/L.By mixing salt solution and the sodium carbonate liquor of 15wt%
It instills in reaction kettle simultaneously, titration time 2h, it is 70 DEG C that reaction temperature is kept in titration process, and divides 4 in precipitation process
Secondary addition 14.4g inertia Al2O3.System pH is controlled 6.0.After salting liquid to be mixed adds, using sodium carbonate liquor by system pH
It is adjusted to 7.5, and the aging 3h at 70 DEG C, is then filtered, washed and by filter cake in 110 DEG C of dry 12h, and in 600 DEG C of roasting 3h.
Obtain 5# heterogeneous catalysis 40Co3O4/7NiO/11Ni/5Co3O4/37Al2O3, heterogeneous catalysis composition in numerical value be corresponding
The mass parts of substance.
Forming and activation: using the fixed bed reactors of Φ 15mm, 5# heterogeneous catalysis tabletting is catalyzed at 5*5mm
Agent is packed into reactor, loadings 10mL, N of the catalyst at 150 DEG C after being broken for 16-30 mesh2Under the conditions of keep 1h, then
It is switched to 300h-1H2In 340 DEG C of reduction 4h.
Activity rating: activity rating method same as Example 1 is used.Reaction carries out 300h, reaction result and catalysis
Agent carbon distribution situation is shown in Table 1.
Embodiment 6
Catalyst is prepared using the precipitation method, 2kg water, 2.6g polyethylene glycol and 15.6gNi powder are added in kettle, is heated to 70
℃.By 239.49g Cr (NO3)3.9H2O、23.57g Co(NO3)2.6H2O、40.5g Ni(NO3)2.6H2O、41.36g Mg
(NO3)2.6H2O、27.37g Ca(NO3)2.4H2O and 200.8g Al (NO3)3.9H2The O mixing soluble in water for being configured to 2mol/L
Salting liquid.The sodium carbonate liquor of mixing salt solution and 15wt% are instilled in reaction kettle simultaneously, titration time 1h, titration process
Middle holding reaction temperature is 70 DEG C, and point 4 addition 11.7g inertia Al in precipitation process2O3, system pH control is 6.0.To
After salting liquid adds, system pH is adjusted to by 7.0, and the aging 3h at 70 DEG C using sodium carbonate liquor, be then filtered, washed and is incited somebody to action
Filter cake is in 110 DEG C of dry 12h, and in 750 DEG C of roasting 3h.Obtain 6# heterogeneous catalysis 35Cr2O3/5MgO/8NiO/12Ni/
5CaO/5Co3O4/30Al2O3, heterogeneous catalysis composition in numerical value be respective substance mass parts.
Forming and activation: using the fixed bed reactors of Φ 15mm, 6# heterogeneous catalysis tabletting is catalyzed at 5*5mm
Agent is packed into reactor, loadings 10mL, N of the catalyst at 150 DEG C after being broken for 16-30 mesh2Under the conditions of keep 1h, then
It is switched to 750h-1H2In 360 DEG C of reduction 4h.
Activity rating: activity rating method same as Example 1 is used.Reaction carries out 300h, reaction result and catalysis
Agent carbon distribution situation is shown in Table 1.
Embodiment 7
Heterogeneous catalysis uses 1# catalyst, and homogeneous catalyst uses CH2I2, CH2I2Dosage be isophorone quality
1%, other Condition Examples 1.
Comparative example 1
Using preparation catalyst, 94.28g Co (NO3)2.6H2O、40.47g Ni(NO3)2.6H2O is dissolved in
In 100ml distilled water, 60 DEG C are heated to, adds 15.6g nickel powder and 78g inertia Al after all dissolutions2O3, the 2h at 60 DEG C,
Flow back 3h, is aged 12h, and filtration washing washes off the ion in solution, 110 DEG C of dry 12h, 600 DEG C of roasting 3h, and it is non-to obtain 7#
Phase catalyst 20Co3O4/12Ni/8NiO/60Al2O3, heterogeneous catalysis composition in numerical value be respective substance mass parts.
Homogeneous catalyst uses CH3I.Shaped catalyst activation and evaluation method are the same as embodiment 1.Reaction carries out 300h, instead
Result and catalyst carbon deposition situation is answered to be shown in Table 1.
Comparative example 2
8# catalyst: commercially available routine 5*5mm Cr2O3/Al2O3Catalyst.Active component Cr2O3Load capacity is 40wt%, is carried
Body accounts for catalyst 60wt%.
Homogeneous catalyst uses CH3I.Feedstock reference implementation example 1.Evaluating catalyst method is the same as embodiment 1.Because of reaction
Carbon distribution is serious, and carbon dust is by reactor plugs, therefore catalyst adds up to have rated 200h, and reaction result and catalyst carbon deposition situation are shown in
Table 1.
Comparative example 3
Catalyst is prepared using the precipitation method, 2kg water is added in kettle, 2.6g polyethylene glycol is heated to 70 DEG C.It will
205.28g Cr(NO3)3.9H2O、23.57g Co(NO3)2.6H2O、27.37g Ca(NO3)2.4H2O and 573.7g Al (NO3)3.9H2The O mixing salt solution soluble in water for being configured to 1.5mol/L.Simultaneously by the sodium carbonate liquor of mixing salt solution and 15wt%
It instills in reaction kettle, titration time 1h, it is 70 DEG C that reaction temperature is kept in titration process, and system pH is controlled 6.5.It is molten to salt
After liquid adds, system pH is adjusted to by 7.5, and the aging 3h at 70 DEG C using sodium carbonate liquor, is then filtered, washed and by filter cake
In 110 DEG C of dry 12h, and in 600 DEG C of roasting 3h.Obtain 9# heterogeneous catalysis 30Cr2O3/5Co3O4/5CaO/60Al2O3, non-equal
Numerical value in phase catalyst composition is the mass parts of respective substance.
Forming and activation: using the fixed bed reactors of Φ 15mm, 9# heterogeneous catalysis tabletting is catalyzed at 5*5mm
Agent is packed into reactor, loadings 10mL, N of the catalyst at 150 DEG C after being broken for 16-30 mesh2Under the conditions of keep 1h, then
It is switched to 500h-1H2In 350 DEG C of reduction 4h.
Activity rating: activity rating method same as Example 1 is used.Because reaction carbon distribution is serious, carbon dust is by reactor
Blocking, therefore catalyst adds up to have rated 200h, reaction result and catalyst carbon deposition situation are shown in Table 1.
Comparative example 4
Catalyst is prepared using the precipitation method, 2kg water is added in kettle, 2.6g polyethylene glycol is heated to 70 DEG C.It will
205.28g Cr(NO3)3.9H2O、23.57g Co(NO3)2.6H2O、75.88g Ni(NO3)2.6H2O、27.37g Ca(NO3)2.4H2O and 301.21g Al (NO3)3.9H2The O mixing salt solution soluble in water for being configured to 1.5mol/L.By mixing salt solution and
The sodium carbonate liquor of 15wt% instills in reaction kettle simultaneously, titration time 1h, and it is 70 DEG C that reaction temperature is kept in titration process,
And point 4 addition 17.6g inertia Al in precipitation process2O3, system pH control is 6.5.After salting liquid adds, using carbonic acid
System pH is adjusted to 7.5, and the aging 3h at 70 DEG C by sodium solution, is then filtered, washed and by filter cake in 110 DEG C of dry 12h, and
In 600 DEG C of roasting 3h.Obtain 10# catalyst 30Cr2O3/15NiO/5Co3O4/5CaO/45Al2O3, heterogeneous catalysis composition in
Numerical value is the mass parts of respective substance.
Forming and activation: using the fixed bed reactors of Φ 15mm, 10# heterogeneous catalysis tabletting is catalyzed at 5*5mm
Agent is packed into reactor, loadings 10mL, N of the catalyst at 150 DEG C after being broken for 16-30 mesh2Under the conditions of keep 1h, then
It is switched to 1000h-1H2In 350 DEG C of reduction 4h.
Activity rating: activity rating method same as Example 1 is used.Reaction carries out 300h, reaction result and catalysis
Agent carbon distribution situation is shown in Table 1.
Comparative example 5
Catalyst is prepared using the precipitation method, 2kg water, 2.6g polyethylene glycol and 15.6gNi powder are added in kettle, is heated to 70
℃.By 273.7g Cr (NO3)3.9H2O、23.57g Co(NO3)2.6H2O、40.47g Ni(NO3)2.6H2O and 200.8g Al
(NO3)3.9H2The O mixing salt solution soluble in water for being configured to 1.5mol/L.By mixing salt solution and the sodium carbonate liquor of 15wt%
It instills in reaction kettle simultaneously, titration time 1h, it is 70 DEG C that reaction temperature is kept in titration process, and divides 4 in precipitation process
Secondary addition 18.2g inertia Al2O3, system pH control is 6.5.After salting liquid to be mixed adds, using sodium carbonate liquor by system pH
It is adjusted to 7.5, and the aging 3h at 70 DEG C, is then filtered, washed and by filter cake in 110 DEG C of dry 12h, and in 600 DEG C of roasting 3h.
Obtain 11# heterogeneous catalysis 40Cr2O3/8NiO/12Ni/5Co3O4/35Al2O3, heterogeneous catalysis composition in numerical value be phase
Answer the mass parts of substance.
Forming and activation: using the fixed bed reactors of Φ 15mm, 11# heterogeneous catalysis tabletting is catalyzed at 5*5mm
Agent is packed into reactor, loadings 10mL, N of the catalyst at 150 DEG C after being broken for 16-30 mesh2Under the conditions of keep 1h, then
It is switched to 500h-1H2In 400 DEG C of reduction 4h.
Activity rating: activity rating method same as Example 1 is used.Reaction carries out 300h, reaction result and catalysis
Agent carbon distribution situation is shown in Table 1.
1 reaction result of table and catalyst carbon deposition situation
Note: carbon distribution content is the weight percentage of carbon distribution on a catalyst；
* it is serious to represent carbon distribution, covers catalyst surface, it can not accurate quantitative analysis.
Claims (15)
1. a kind of heterogeneous catalysis, comprising active component, carrier and optional auxiliary agent, the active component include Ni, NiO,
Cr2O3And Co3O4；
The content of the Ni is 5-20wt%；The content of NiO is 5-20wt%；Cr2O3And Co3O4Content be 15-50wt%；It helps
The content of agent is 0~20wt%；The content of the carrier is 30-70wt%, is calculated on the basis of heterogeneous catalysis gross mass；
The mass ratio of the Ni and NiO is 2:3-3:1；
The Cr2O3With Co3O4Mass ratio be 3:5-9:1；
The heterogeneous catalysis, preparation method includes the following steps:
(1) water is added into reaction kettle, expanding agent and Ni powder is then added, is heated to 40-120 DEG C；
(2) proportionally, chromic salts, cobalt salt, nickel salt, the salt of auxiliary agent, aluminium salt are dissolved in distilled water, it is water-soluble that salt-mixture is made
Mixed-salt aqueous solution is added in reaction kettle with alkaline precipitating agent cocurrent and precipitates by liquid, inertia Al2O3Precipitating is added portionwise
In system, 60-90 DEG C of precipitation process temperature, pH 5.0-8.0, sedimentation time 1-3h are controlled, mixing salt solution uses alkali after adding
System pH is adjusted to 7.0-9.0 by property precipitating reagent, then obtains slurry in 60-90 DEG C of aging 1-3h；
(3) slurry is through being filtered, washed, and in 80-120 DEG C of dry 8-16h, and in 600-900 DEG C of roasting 2-8h, is made described non-equal
Phase catalyst.
2. heterogeneous catalysis according to claim 1, which is characterized in that the content of the Ni is 6-15wt%；NiO's
Content is 7-15wt%；Cr2O3And Co3O4Content be 35-45wt%；The content of auxiliary agent is 5~10wt%；The carrier
Content is 35-45wt%, is calculated on the basis of heterogeneous catalysis gross mass.
3. heterogeneous catalysis according to claim 1, which is characterized in that the mass ratio of the Ni and NiO is 3:4-3:
2。
4. heterogeneous catalysis according to claim 1, which is characterized in that the Cr2O3With Co3O4Mass ratio be 6:1-
8:1。
5. heterogeneous catalysis according to claim 1, which is characterized in that the auxiliary agent is selected from alkali and alkaline earth metal ions
One of oxide is a variety of.
6. heterogeneous catalysis according to claim 1, which is characterized in that the auxiliary agent is selected from one of CaO and MgO
Or two kinds.
7. heterogeneous catalysis according to claim 1, which is characterized in that the carrier is selected from SiO2、Al2O3、ZrO2, point
Son sieve and TiO2One of or it is a variety of.
8. heterogeneous catalysis according to claim 1, which is characterized in that the carrier is selected from γ-Al2O3And inertia
Al2O3Mixture.
9. heterogeneous catalysis according to claim 8, which is characterized in that the γ-Al2O3With inertia Al2O3Mixing
Inertia Al in object2O3Account for γ-Al2O3And inertia Al2O3The 20-50wt% of total weight.
10. heterogeneous catalysis according to claim 1, which is characterized in that the temperature of heating is in the step (1)
60-90℃。
11. heterogeneous catalysis according to claim 1, which is characterized in that the heterogeneous catalysis is at 330-380 DEG C
Reduction activation.
12. heterogeneous catalysis according to claim 11, which is characterized in that the heterogeneous catalysis is in 340-360
DEG C reduction activation.
13. a kind of method of isophorone preparation 3,5-dimethylphenol comprising the steps of: in inert gas and CO2Atmosphere
In, it is reacted under the catalysis of heterogeneous catalysis and homogeneous catalyst of the isophorone described in claim 11, reaction temperature
Degree is 350-700 DEG C, reaction pressure 0-2MPa.
14. according to the method for claim 13, which is characterized in that the CO2Volume fraction be 0.05-2%, with inertia
The volume of gas calculates.
15. according to the method for claim 13, which is characterized in that the CO2Volume fraction be 0.5-1%, with indifferent gas
The volume of body calculates.
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| CN112547104B (en) * | 2020-12-01 | 2022-09-20 | 万华化学集团股份有限公司 | Heterogeneous catalyst for preparing 3, 5-dimethylphenol from isophorone, and preparation method and application thereof |
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| CN1198430A (en) * | 1997-05-03 | 1998-11-11 | 吕特格焦油加工股份公司 | Process for preparing 3,5-dimethylphenol |
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