CN108906061A - A kind of nickel-base catalyst and its application in production space bulky amine tert-butylamine base oxethyl ethyl alcohol - Google Patents
A kind of nickel-base catalyst and its application in production space bulky amine tert-butylamine base oxethyl ethyl alcohol Download PDFInfo
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7676—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
Abstract
A kind of nickel-base catalyst and its application in the desulfurization solvent tert-butylamine base oxethyl ethyl alcohol that catalysis diethylene glycol (DEG) and tert-butylamine amination generation have serious space steric effect, belong to heterogeneous catalysis amination field.Be will on nickel salt solution incipient impregnation to 1~3g carrier, impregnate 0.5~for 24 hours, the pore volume of carrier and the volume of nickel salt solution are identical；Be placed under 50~85 DEG C of water bath conditions and be evaporated again, then under the conditions of 100~120 DEG C drying 2~for 24 hours；0.5~8h is roasted under 250~650 DEG C of air atmospheres, and the nickel-base catalyst presoma is made；Finally in H2Under the conditions of/Ar gaseous mixture, 300~600 DEG C of 0.5~8h of reduction obtain nickel-base catalyst of the present invention.The present invention uses preparation catalyst, and simple process is suitble to large-scale industrial production.Catalyst of the invention is applied to fixed-bed reactor, and TBEE selectively can reach 98.6%；Catalyst of the invention is applied in batch tank reactor, and DEG high conversion rate is up to 93.0%.
Description
Technical field
The invention belongs to heterogeneous catalysis amination fields, and in particular to a kind of nickel-base catalyst and its in catalysis diethylene glycol (DEG) and uncle
Butylamine amination generates the application in the desulfurization solvent tert-butylamine base oxethyl ethyl alcohol with serious space steric effect.
Background technique
Tert-butylamine base oxethyl ethyl alcohol (TBEE) is as a kind of organic amine with serious space steric effect in sour gas
Body processing aspect has good application, especially in processing peracidity CO2/H2In terms of the desulfurization of S mixed gas, than traditional desulfurization
The advantages that solvent methyl diethanol amine (MDEA) desulfuration selectivity is more preferable, and sour gas load is big.
It is had been reported in pertinent literature and patent and catalyzes and synthesizes serious sterically hindered amines TBEE, at high temperature under high pressure, selected
It is used to be catalyzed diethylene glycol (DEG) (DEG) and tert-butylamine with the catalyst that the metal or noble metal that add hydrogen dehydrogenation activity are prepared
(TBA) reaction synthesis TBEE, reaction condition require stringent, the high requirements on the equipment.
In the patent of invention CN1922128B of ExxonMobil Research Engineering Company, the catalysis for meeting commercial requirement is used
Agent, in a kettle, catalysis diethylene glycol (DEG) are reacted with tert-butylamine.It was found that activation temperature is high, activity is good, and initial pressure is low, activity compared with
Height, TBA:DEG molar ratio is high, and selectivity is good.Meanwhile in this patent of invention, active specy load capacity is high, available after reduction
Amount is few, and the selectivity of TBEE reduces obviously with the reaction time.In another patent of ExxonMobil Research Engineering Company
In CN100572355C, to preparation 19.5%Ni-MCM41/ aluminium oxide nickel-base catalyst during whether there is or not the progress of TEA additive
Comparison, the activity for the catalyst that discovery has TEA to add are apparently higher than the catalytic activity of the catalyst of no TEA addition；Compare three kinds
The catalyst of different carriers：(about 65%Ni is deposited 19.5%Ni-MCM41/ aluminium oxide catalyst, the E480-P for having TEA to add
Nickel-base catalyst on to carrier), Ni5132-P (about 60% deposits on carrier), have TEA add 19.5%Ni-
For conversion ratio compared with E480-P high, selectivity is good compared with Ni5132-P under lower nickel loading for MCM41/ aluminium oxide catalyst, but this
Catalyst preparation process is complicated in patented invention, causes process costs to increase, is unfavorable for large-scale industrial production.
Pass through addition differential responses medium in Chinese patent CN1623978A：Water, methanol, ethyl alcohol are one such to reaction
It is catalyzed 2- chloroethoxyethanol and tert-butylamine reaction in kettle and prepares tert-butylamine base oxethyl ethyl alcohol, under conditions of not adding catalyst
Production method need to by pressurizeing, neutralizing, slightly evaporate, the processes such as rectifying, production technology complexity is unfavorable for industrializing extensive life
It produces.
It is disclosed in reaction kettle in United States Patent (USP) US4487967, reaction raw materials TBA：DEG molar ratio is 1：1 premise
Under, various carrier-free metal (single metal or more metals) catalyst diethylene glycol (DEG)s (DEG) react synthesis with tert-butylamine (TBA)
TBEE, TBEE yield highest 34%.In the case where having carrier loaded, with the raising of nickel loading, TBEE yield is improved,
When nickel loading reaches 65%, TBEE yield only 54%.More active specy loss in reaction process, the production cost increases.
It is reacted in United States Patent (USP) US453452 using halogenated alkanol, requirement of the formation and removal of halide to equipment
Height needs corrosion-resistant.Meanwhile the later period reaches purification purpose to the absorption of halide using lye, increases production cost, it is raw
At chloride also affect to environment.There is also such defects by United States Patent (USP) US339892.
Summary of the invention
It is prepared the object of the present invention is to provide a kind of nickel-base catalyst and its in catalysis tert-butylamine and diethylene glycol (DEG) amination serious
Sterically hindered amines --- the application in tert-butylamine base oxethyl ethyl alcohol (TBEE), using preparation catalyst, simple process,
It is suitble to large-scale industrial production.Catalyst of the invention is applied to fixed-bed reactor, and TBEE selectively can reach
98.6%；Catalyst of the invention is applied in batch tank reactor, and DEG high conversion rate is up to 93.0%.
In order to achieve the above objectives, the technical solution adopted by the present invention is that：
A kind of Supported Nickel Catalyst, is prepared with infusion process, and load capacity is 2~50wt%, and carrier is selected from SiO2、Al2O3
(business or self-control), TiO2, MgO, active carbon, MCM-22, MCM-41, ZSM-5, SBA-15,6201 carriers, in 102 carriers
It is a kind of.
A kind of preparation method of nickel-base catalyst of the present invention, its step are as follows：
1) nickel salt is dissolved in distilled water, stirring to dissolution, nickel salt concentration range 5 × 10-4~5.0moL/L；
2) will on nickel salt solution incipient impregnation to 1~3g carrier, impregnate 0.5~for 24 hours, the pore volume and nickel salt of carrier are molten
The volume of liquid is identical；
3) sample for obtaining step 2) is placed under 50~85 DEG C of water bath conditions and is evaporated, then under the conditions of 100~120 DEG C
Drying 2~for 24 hours；
4) sample obtained after step 3) drying is roasted under 250~650 DEG C of air atmospheres 0.5~8h, is made described
Nickel-base catalyst presoma；
5) by the resulting nickel-base catalyst presoma of step 4) in H2Under the conditions of/Ar gaseous mixture, 300~600 DEG C of reduction 0.5
~8h obtains nickel-base catalyst of the present invention.
The method of reduction is in step 5)：
1. in fixed bed reactors carry out in-situ reducing method, be fixed bed reactors flat-temperature zone be added with
The nickel-base catalyst presoma that diamond dust mixes in equal volume, diamond dust is filled at remaining position of reactor, in 300~600 DEG C, H2/
Ar gaseous mixture (H2Percentage by volume 8~15%) under the conditions of 0.5~8h of in-situ reducing, be cooled to 180~300 DEG C, obtain Ni-based
Catalyst；
2. and the method for being restored in batch tank reactor, be to take appropriate nickel-base catalyst presoma in quartz
Guan Zhong, in 300~600 DEG C, H2/ Ar gaseous mixture (H2Percentage by volume 8~15%) under the conditions of restore 0.5~8h, after reduction
It is down to room temperature, obtains nickel-base catalyst.
Diethylene glycol (DEG) is catalyzed in fixed bed reactors using nickel-base catalyst described above and is prepared by tert-butylamine amination condensation
TBEE, reaction condition are：1.5mL catalyst mixes down in equal volume with diamond dust, and reaction temperature is 180~300 DEG C, and reaction solution is
Tert-butylamine and diethylene glycol (DEG) molar ratio are 0.5~10：1 mixed solution, Liquid sample introduction amount are 0.5~20mL/h, switching before reacting
Reducing atmosphere is reaction atmosphere, and pressure is 0.5~5MPa.
Diethylene glycol (DEG) is catalyzed in batch tank reactor using nickel-base catalyst described above and tert-butylamine amination condensation is made
Standby TBEE, reaction condition are：Catalyst amount is 1~2wt% of reaction mixture, and reaction solution is tert-butylamine and diethylene glycol (DEG) mole
Than being 0.5~10：1 mixed solution, reaction temperature are 180~300 DEG C, and adjusting Hydrogen Vapor Pressure is 0.5~3MPa.
Compared with prior art, advantage of the invention is that：
1) catalyst composition of the present invention and preparation method are simple, and raw material is easy to get, at low cost；
2) it is prepared using equi-volume impregnating, active component is uniformly dispersed, and calculation is more in effective active, and activity is good；
3) catalyst of the present invention can be applied in fixed bed and batch tank reactor simultaneously；
4) catalyst of the present invention is applied to flow reactor of fixed bed, and continuous feed, activity is high, TBEE selectivity
Height, catalyst performance stabilised are suitable for industrialized production；
5) reactivity worth in fixed bed is obviously improved compared with reaction kettle, and initial activity is high compared with reaction kettle, and performance
Stablize easily recycling, it is reusable；
6) it is produced in fixed bed reactors, TBEE selectivity highest can achieve 98.6%；In batch tank reactor,
DEG conversion ratio highest can achieve 93.0%.
Specific embodiment
Technical solution of the present invention is described in further detail below in conjunction with specific embodiment, but the embodiment does not limit
Protection scope of the present invention.
Embodiment 1
Weigh 1.14g Ni (NO3)2·6H2O adds distilled water 2.2mL, stirring and dissolving, by solution homogeneous impregnation in 2g 40-
60 mesh SiO2(pore volume of carrier is estimated indirectly by surveying the water absorption rate of carrier to carrier, and there is no the numerical value determined, is led to
The water absorption rate of measurement carrier is crossed to determine nickel salt solution volume) on, 2h is impregnated, is then placed on 85 DEG C of water-baths and dries, set
In 100 DEG C of oven overnights, 400 DEG C of roasting 4h under air atmosphere, obtain 10wt%Ni/SiO in Muffle furnace2Complex catalyst precursor
Body.It takes 1.5mL catalyst precursor to mix in equal volume with diamond dust, is placed in fixed bed reactors, at 360 DEG C, 10% (volume
Score) H2In-situ reducing 2h under/Ar gaseous mixture 0.4MPa, obtains 10wt%Ni/SiO2Catalyst.It is cooled to after reduction anti-
Temperature is answered, produces reacting for TBEE with tert-butylamine amination for being catalyzed diethylene glycol (DEG).It reacts and gas circuit is switched to hydrogen gas before starting
Road, reaction pressure 2MPa, reaction temperature are 250 DEG C, and reaction solution is tert-butylamine and diethylene glycol (DEG) molar ratio is 2：1 mixing is molten
Liquid, Liquid sample introduction amount are 6mL/h, react 6h, the conversion ratio of DEG is that the selectivity of 23.5%, TBEE is the receipts of 65.8%, TBEE
Rate is 15.5%.
Take above-mentioned 10wt%Ni/SiO2Catalyst precursor powder 0.25g is in quartz ampoule, and 360 DEG C, 10% (volume point
Number) H2Reductase 12 h under/Ar gaseous mixture 0.4MPa, obtains 10wt%Ni/SiO2Catalyst.Room temperature is down to after reduction, between being used for
Catalysis diethylene glycol (DEG) of having a rest in tank reactor with tert-butylamine amination produces reacting for TBEE.It reacts and tert-butylamine is added in forward reaction kettle
It is 2 with diethylene glycol (DEG) molar ratio：1 mixed solution, adds catalyst, and adjusting Hydrogen Vapor Pressure is 0.5Mpa, reaction temperature 230
DEG C, 8h is reacted, the conversion ratio of DEG is up to 51.5%, TBEE selectively up to 84.8%.
Embodiment 2
Weigh 0.644g Ni (NO3)2·6H2O adds distilled water 2mL, stirring and dissolving, by solution homogeneous impregnation in 2g 40-
60 mesh SiO2On carrier, 2h is impregnated, is then placed on 85 DEG C of water-baths and dries, 100 DEG C of oven overnights are placed in, in Muffle furnace
The lower 400 DEG C of roastings 4h of air atmosphere, obtains 6wt%Ni/SiO2Catalyst precursor, take catalyst precursor powder 0.25g in
In quartz ampoule, 360 DEG C, 10% (volume fraction) H2Reductase 12 h under/Ar gaseous mixture 0.4MPa, obtains 6wt%Ni/SiO2Catalyst.
It is down to room temperature after reduction, produces reacting for TBEE with tert-butylamine amination for being catalyzed diethylene glycol (DEG) in batch tank reactor.
Reacting addition tert-butylamine and diethylene glycol (DEG) molar ratio in forward reaction kettle is 2：1 mixed solution, adds catalyst,
Adjusting Hydrogen Vapor Pressure is 0.5Mpa, 230 DEG C of reaction temperature, reacts 8h, the conversion ratio of DEG is up to 39.2%, TBEE selectivity
Up to 78.4%.
Embodiment 3
Weigh 2.658g Ni (NO3)2·6H2O adds distilled water 1mL, stirring and dissolving, by solution homogeneous impregnation in 2g 40-
On 60 mesh absorbent charcoal carriers, 2h is impregnated, is then placed on 85 DEG C of water-baths and dries, 100 DEG C of oven overnights are placed in, in Muffle furnace
The interior lower 400 DEG C of roastings 4h of air atmosphere, obtains 20wt%Ni/C catalyst precursor.Take 1.5mL catalyst precursor and Buddha's warrior attendant
Sand mixes in equal volume, is placed in fixed bed reactors, at 360 DEG C, 10% (volume fraction) H2It is restored under/Ar gaseous mixture 0.4MPa
2h obtains 20wt%Ni/C catalyst.It is down to reaction temperature after reduction, is produced for being catalyzed diethylene glycol (DEG) with tert-butylamine amination
The reaction of TBEE.It reacts and gas circuit is switched to 25%H before starting2/ Ar gaseous mixture, reaction pressure 2MPa, reaction temperature 250
DEG C, reaction solution is tert-butylamine and diethylene glycol (DEG) molar ratio is 2：1 mixed solution, Liquid sample introduction amount are 6mL/h, react 6h, DEG's
The yield that the selectivity that conversion ratio is 14.2%, TBEE is 94.1%, TBEE is 13.3%.
Embodiment 4
Weigh 2.658g Ni (NO3)2·6H2O adds distilled water 1.9mL, stirring and dissolving, by solution homogeneous impregnation in 2g
On absorbent charcoal carrier after 40-60 mesh 6mol/L nitric acid treatment, 2h is impregnated, is then placed on 85 DEG C of water-baths and dries, set
In 100 DEG C of oven overnights, 400 DEG C of roasting 4h under air atmosphere, obtain 20wt%Ni/C catalyst precursor in Muffle furnace.It takes
1.5mL catalyst precursor mixes in equal volume with diamond dust, is placed in fixed bed reactors, at 360 DEG C, 10% (volume fraction)
H2Reductase 12 h under/Ar gaseous mixture 0.4MPa, obtains 20wt%Ni/C catalyst.Reaction temperature is down to after reduction, for urging
Change diethylene glycol (DEG) and produces reacting for TBEE with tert-butylamine amination.It reacts and gas circuit is switched to 25%H before starting2/ Ar gaseous mixture, reaction
Pressure is 2MPa, and reaction temperature is 250 DEG C, and reaction solution is tert-butylamine and diethylene glycol (DEG) molar ratio is 2：1 mixed solution, liquid into
Sample amount is 6mL/h, reacts 6h, and the yield that the selectivity that the conversion ratio of DEG is 26.3%, TBEE is 89.9%, TBEE is
23.6%.
Embodiment 5
Weigh 1.9936g Ni (NO3)2·6H2O adds distilled water 2.8mL, stirring and dissolving, by solution homogeneous impregnation in 1.5g
On 40-60 mesh SBA-15 carrier, 2h is impregnated, is then placed on 85 DEG C of water-baths and dries, 100 DEG C of oven overnights are placed in, in horse
The not lower 400 DEG C of roastings 4h of furnace air atmosphere, obtains 20wt%Ni/SBA-15 catalyst precursor.Take 1.5mL complex catalyst precursor
Body mixes in equal volume with diamond dust, is placed in fixed bed reactors, at 360 DEG C, 10% (volume fraction) H2/ Ar gaseous mixture
Reductase 12 h under 0.4MPa obtains 20wt%Ni/SBA-15 catalyst.Reaction temperature is down to after reduction, it is sweet for being catalyzed two
Alcohol produces reacting for TBEE with tert-butylamine amination.It reacts and gas circuit is switched to 25%H before starting2/ Ar gaseous mixture, reaction pressure are
2MPa, reaction temperature are 250 DEG C, and reaction solution is tert-butylamine and diethylene glycol (DEG) molar ratio is 2：1 mixed solution, Liquid sample introduction amount are
6mL/h reacts 6h, and the yield that the selectivity that the conversion ratio of DEG is 27.2%, TBEE is 89.7%, TBEE is 24.4%.
Embodiment 6
Weigh 2.658g Ni (NO3)2·6H2O adds distilled water 4.5mL, stirring and dissolving, by solution homogeneous impregnation in 2g
On 40-60 mesh MCM-41 carrier, 2h is impregnated, is then placed on 85 DEG C of water-baths and dries, 100 DEG C of oven overnights are placed in, in horse
The not lower 400 DEG C of roastings 4h of furnace air atmosphere, obtains 20wt%Ni/MCM-41 catalyst precursor.Take 1.5mL complex catalyst precursor
Body mixes in equal volume with diamond dust, is placed in fixed bed reactors, at 360 DEG C, 10% (volume fraction) H2/ Ar gaseous mixture
Reductase 12 h under 0.4MPa obtains 20wt%Ni/MCM-41 catalyst.Reaction temperature is down to after reduction, it is sweet for being catalyzed two
Alcohol produces reacting for TBEE with tert-butylamine amination.It reacts and gas circuit is switched to 25%H before starting2/ Ar gaseous mixture, reaction pressure are
2MPa, reaction temperature are 250 DEG C, and reaction solution is tert-butylamine and diethylene glycol (DEG) molar ratio is 2：1 mixed solution, Liquid sample introduction amount are
6mL/h reacts 6h, and the yield that the selectivity that the conversion ratio of DEG is 3.6%, TBEE is 98.6%, TBEE is 3.6%.
Embodiment 7
Weigh 1.9936g Ni (NO3)2·6H2O adds distilled water 2.5mL, stirring and dissolving, by solution homogeneous impregnation in 1.5g
On 40-60 mesh MCM-22 carrier, 2h is impregnated, is then placed on 85 DEG C of water-baths and dries, 100 DEG C of oven overnights are placed in, in horse
The not lower 400 DEG C of roastings 4h of furnace air atmosphere, obtains 20wt%Ni/MCM-22 catalyst precursor.Take 1.5mL complex catalyst precursor
Body mixes in equal volume with diamond dust, is placed in fixed bed reactors, at 360 DEG C, 10% (volume fraction) H2/ Ar gaseous mixture
Reductase 12 h under 0.4MPa obtains 20wt%Ni/MCM-22 catalyst.Reaction temperature is down to after reduction, it is sweet for being catalyzed two
Alcohol produces reacting for TBEE with tert-butylamine amination.It reacts and gas circuit is switched to 25%H before starting2/ Ar gaseous mixture, reaction pressure are
2MPa, reaction temperature are 250 DEG C, and reaction solution is tert-butylamine and diethylene glycol (DEG) molar ratio is 2：1 mixed solution, Liquid sample introduction amount are
6mL/h reacts 6h, and the yield that the selectivity that the conversion ratio of DEG is 26.6%, TBEE is 95.7%, TBEE is 25.5%.
Comparative example 1
Micro porous molecular sieve ZSM-5 molecular sieve is selected, compared with Mesoporous silica MCM 41, MCM-22 etc., investigates molecular sieve pores
Diameter reacts influence to what TBEE was produced in diethylene glycol (DEG) and tert-butylamine amination.Weigh 2.658gNi (NO3)2·6H2O adds distilled water
1.0mL, stirring and dissolving impregnate 2h, are then placed into 85 DEG C of water by solution homogeneous impregnation on 2g 40-60 mesh ZSM-5 carrier
It is dried on bath, is placed in 100 DEG C of oven overnights, 400 DEG C of roasting 4h under air atmosphere, obtain 20wt%Ni/ in Muffle furnace
ZSM-5 catalyst precursor.It takes 1.5mL catalyst precursor to mix in equal volume with diamond dust, is placed in fixed bed reactors,
360 DEG C, 10% (volume fraction) H2Reductase 12 h under/Ar gaseous mixture 0.4MPa, obtains 20wt%Ni/ZSM-5 catalyst.Reduction knot
It is down to reaction temperature after beam, produces reacting for TBEE with tert-butylamine amination for being catalyzed diethylene glycol (DEG).Reaction item same as Example 7
Under part, the yield that the selectivity that the conversion ratio of DEG is 0.3%, TBEE is 56.7%, TBEE is 0.2%.Micro porous molecular sieve ZSM-
5 aperture is significantly less than Mesoporous silica MCM 41, MCM-22, and reactant diethylene glycol (DEG) makees the catalyst of carrier in micro porous molecular sieve
On, conversion ratio is very low.
Embodiment 8
Weigh 1.135g Ni (NO3)2·6H2O adds distilled water 1.7mL, stirring and dissolving, by solution homogeneous impregnation in 2g
On 40-60 mesh MgO carrier, 2h is impregnated, is then placed on 80 DEG C of water-baths and dries, 100 DEG C of oven overnights are placed in, in Muffle furnace
The interior lower 400 DEG C of roastings 4h of air atmosphere, obtains 10wt%Ni/MgO catalyst precursor, takes catalyst precursor powder 0.25g
In quartz ampoule, 360 DEG C, 10% (volume fraction) H2Reductase 12 h under/Ar gaseous mixture 0.4MPa obtains 10wt%Ni/MgO catalysis
Agent.It is down to room temperature after reduction, produces the anti-of TBEE with tert-butylamine amination for being catalyzed diethylene glycol (DEG) in batch tank reactor
It answers.
Reacting addition tert-butylamine and diethylene glycol (DEG) molar ratio in forward reaction kettle is 2：1 mixed solution, adds catalyst,
Adjusting Hydrogen Vapor Pressure is 0.5Mpa, 230 DEG C of reaction temperature, reacts 8h, the conversion ratio of DEG is up to 7.6%, TBEE selectivity most
Up to 3.9%.
Embodiment 9
Weigh 1.14g Ni (NO3)2·6H2O adds distilled water 1.5mL, stirring and dissolving, by solution homogeneous impregnation in 2g 40-
60 mesh TiO2On carrier, 2h is impregnated, is then placed on 80 DEG C of water-baths and dries, 100 DEG C of oven overnights are placed in, in Muffle furnace
The lower 400 DEG C of roastings 4h of air atmosphere, obtains 10wt%Ni/TiO2Catalyst precursor, take catalyst precursor powder 0.25g in
In quartz ampoule, 360 DEG C, 10% (volume fraction) H2Reductase 12 h under/Ar gaseous mixture 0.4MPa, obtains 10wt%Ni/TiO2Catalysis
Agent.It is down to room temperature after reduction, produces the anti-of TBEE with tert-butylamine amination for being catalyzed diethylene glycol (DEG) in batch tank reactor
It answers.
Reacting addition tert-butylamine and diethylene glycol (DEG) molar ratio in forward reaction kettle is 2：1 mixed solution, adds catalyst,
Adjusting Hydrogen Vapor Pressure is 0.5Mpa, 230 DEG C of reaction temperature, reacts 8h, the conversion ratio of DEG is up to 43.5%, TBEE selectivity
Up to 75.0%.
Embodiment 10
Weigh 1.135g Ni (NO3)2·6H2O adds distilled water 2.5mL, stirring and dissolving, by solution homogeneous impregnation in 2g
On 6201 carrier of 40-60 mesh, 2h is impregnated, is then placed on 85 DEG C of water-baths and dries, 100 DEG C of oven overnights are placed in, in Muffle
The lower 400 DEG C of roastings 4h of furnace air atmosphere, obtains 10wt%Ni/6201 carrier catalyst precursor.Take 1.5mL complex catalyst precursor
Body mixes in equal volume with diamond dust, is placed in fixed bed reactors, at 360 DEG C, 10% (volume fraction) H2/ Ar gaseous mixture
Reductase 12 h under 0.4MPa obtains 10wt%Ni/6201 carrier catalyst.Reaction temperature is down to after reduction, for being catalyzed two
Glycol produces reacting for TBEE with tert-butylamine amination.It reacts and gas circuit is switched to 35%H before starting2/ Ar gaseous mixture, reaction pressure
For 2MPa, reaction temperature is 250 DEG C, and reaction solution is tert-butylamine and diethylene glycol (DEG) molar ratio is 2：1 mixed solution, Liquid sample introduction amount
For 6mL/h, 6h is reacted, the yield that the selectivity that the conversion ratio of DEG is 7.7%, TBEE is 40.7%, TBEE is 3.1%.
Take above-mentioned 10wt%Ni/6201 carrier catalyst precursor powder 0.25g in quartz ampoule, 360 DEG C, 10% (body
Fraction) H2Reductase 12 h under/Ar gaseous mixture 0.4MPa, obtains 10wt%Ni/6201 catalyst.Room temperature is down to after reduction,
Reacting for TBEE is produced with tert-butylamine amination for being catalyzed diethylene glycol (DEG) in batch tank reactor.It reacts in forward reaction kettle and is added
Tert-butylamine and diethylene glycol (DEG) molar ratio are 2：1 mixed solution, adds catalyst, and adjusting Hydrogen Vapor Pressure is 0.5Mpa, reaction temperature
230 DEG C of degree, reacts 8h, and the conversion ratio of DEG is up to 39.9%, TBEE selectively up to 51.6%.
Embodiment 11
Weigh 1.14g Ni (NO3)2·6H2O adds distilled water 3.5mL, stirring and dissolving, by solution homogeneous impregnation in 2g 40-
On 60 mesh, 102 carrier, 2h is impregnated, is then placed on 85 DEG C of water-baths and dries, 100 DEG C of oven overnights are placed in, in Muffle furnace
The lower 400 DEG C of roastings 4h of air atmosphere, obtains 10wt%Ni/102 carrier catalyst precursor.Take 1.5mL catalyst precursor with
Diamond dust mixes in equal volume, is placed in fixed bed reactors, at 360 DEG C, 10% (volume fraction) H2Under/Ar gaseous mixture 0.4MPa
Reductase 12 h obtains 10wt%Ni/102 carrier catalyst.Reaction temperature is down to after reduction, for being catalyzed diethylene glycol (DEG) and tertiary fourth
The reaction of TBEE is produced in amine amination.It reacts and gas circuit is switched to 35%H before starting2/ Ar gaseous mixture, reaction pressure 2MPa, instead
Answering temperature is 250 DEG C, and reaction solution is tert-butylamine and diethylene glycol (DEG) molar ratio is 2：1 mixed solution, Liquid sample introduction amount are 6mL/h,
6h is reacted, the yield that the selectivity that the conversion ratio of DEG is 16.4%, TBEE is 68.7%, TBEE is 11.3%.
Take above-mentioned 10wt%Ni/102 carrier catalyst precursor powder 0.25g in quartz ampoule, 360 DEG C, 10% (volume
Score) H2Reductase 12 h under/Ar gaseous mixture 0.4MPa, obtains 10wt%Ni/102 catalyst.It is down to room temperature after reduction, is used for
It is catalyzed diethylene glycol (DEG) in batch tank reactor and produces reacting for TBEE with tert-butylamine amination.It reacts and tertiary fourth is added in forward reaction kettle
Amine and diethylene glycol (DEG) molar ratio are 2：1 mixed solution, adds catalyst, and adjusting Hydrogen Vapor Pressure is 0.5Mpa, reaction temperature 230
DEG C, 8h is reacted, the conversion ratio of DEG is up to 22.6%, TBEE selectively up to 66.3%.
Embodiment 12
Weigh 2.658g Ni (NO3)2·6H2O adds distilled water to dissolve, by solution homogeneous impregnation in 2g 40-60 mesh SiO2
On carrier, 2h is impregnated, is then placed on 85 DEG C of water-baths and dries, be placed in 100 DEG C of oven overnights, the air atmosphere in Muffle furnace
Lower 400 DEG C of roastings 4h, obtains 20wt%Ni/SiO2Catalyst precursor takes catalyst precursor powder 0.25g in quartz ampoule
In, 10% (volume fraction) H2/ Ar gaseous mixture 0.4MPa, different reduction temperature (260 DEG C, 360 DEG C, 460 DEG C, 560 DEG C) conditions
Lower reductase 12 h, obtained catalyst precursor and catalyst are denoted as A, B, C, D, E respectively.It is down to room temperature after reduction, is used for
It is catalyzed diethylene glycol (DEG) in batch tank reactor and produces reacting for TBEE with tert-butylamine amination.It reacts and tertiary fourth is added in forward reaction kettle
Amine and diethylene glycol (DEG) molar ratio are 2：1 mixed solution, adds catalyst, and adjusting Hydrogen Vapor Pressure is 0.5Mpa, reaction temperature 230
DEG C, react 8h, reaction result such as the following table 1：
Table 1：Diethylene glycol (DEG) and tert-butylamine aminating reaction Evaluation results on the catalyst of different temperatures reduction
Embodiment 13
Weigh 2.658g Ni (NO3)2·6H2O adds distilled water 3mL, stirring and dissolving, by solution homogeneous impregnation in 2g 40-
60 mesh Al2O3On carrier (business), 2h is impregnated, is then placed on 85 DEG C of water-baths and dries, 100 DEG C of oven overnights are placed in, in horse
The not lower 400 DEG C of roastings 4h of furnace air atmosphere, obtains 20wt%Ni/Al2O3Catalyst precursor.Take 1.5mL catalyst precursor
It mixes, is placed in fixed bed reactors in equal volume with diamond dust, at 360 DEG C, 10% (volume fraction) H2/ Ar gaseous mixture 0.4MPa
Lower reductase 12 h, obtains 20wt%Ni/Al2O3Catalyst.Reaction temperature is down to after reduction, for being catalyzed diethylene glycol (DEG) and tertiary fourth
The reaction of TBEE is produced in amine amination.It reacts and gas circuit is switched to 25%H before starting2/ Ar gaseous mixture, reaction pressure 2MPa, instead
Answering temperature is 250 DEG C, and reaction solution is tert-butylamine and diethylene glycol (DEG) molar ratio is 2：1 mixed solution, Liquid sample introduction amount are 6mL/h,
6h is reacted, the yield that the selectivity that the conversion ratio of DEG is 35.2%, TBEE is 89.8%, TBEE is 31.6%.
Comparative example 2
Ammonium hydroxide makees precipitating reagent, and aluminum nitrate is silicon source, with ammonia water titration to pH=9 while stirring at room temperature, continues to stir
2h, then places 12h under 85 DEG C of water bath conditions, and 100 DEG C of baking ovens 18h, 600 DEG C of roasting 4h obtain Al2O3.Weigh 1.14g Ni
(NO3)2·6H2O adds distilled water 1.6mL, stirring and dissolving, by nickel salt solution homogeneous impregnation in the made Al of 2g 40-60 mesh2O3Carrier
On, it is then placed on 80 DEG C of water-baths and dries, be placed in 100 DEG C of oven overnights, 400 DEG C of roastings under air atmosphere in Muffle furnace
4h obtains 10wt%Ni/Al2O3Catalyst precursor.It takes 1.5mL catalyst precursor to mix in equal volume with diamond dust, is placed in solid
In fixed bed reactor, at 360 DEG C, 10% (volume fraction) H2Reductase 12 h under/Ar gaseous mixture 0.4MPa, obtains 10wt%Ni/
Al2O3Catalyst.It is down to reaction temperature after reduction, produces reacting for TBEE with tert-butylamine amination for being catalyzed diethylene glycol (DEG).With
Under 13 same reaction conditions of embodiment, the conversion ratio of diethylene glycol (DEG) is that the selectivity of 11.6%, TBEE is the yield of 52.1%, TBEE
It is 6.0%.In fixed bed reaction system, compared with commercial aluminum oxide makees the catalyst of carrier preparation, homemade three oxygen
Changing two aluminium and making the conversion ratio of DEG and the selectivity of TBEE and yield on the catalyst of carrier preparation has apparent reduction.Carrier
Structure, property have apparent influence to the catalytic performance of catalyst.
Comparative example 3
20wt%Ni-Al is prepared using coprecipitation2O3Catalyst：Weigh 3.39g Ni (NO3)2·6H2O, 18.76g Al
(NO3)3·9H2O adds distilled water stirring and dissolving, mixes to round-bottomed flask, stirs under 80 DEG C of water bath conditions and uses 0.5mol/L
Na2CO3Solution is titrated to pH=9, continues to stir 2h, still aging 2h, then filtering and washing to neutrality, gained filter cake is put into
100 DEG C of oven overnights, 450 DEG C of roasting 3h, obtain 20wt%Ni-Al2O3Catalyst precursor.Take 0.3g catalyst precursor with
The mass mixings such as diamond dust, are placed in fixed bed reactors, at 650 DEG C, 10% (volume fraction) H2Under/Ar gaseous mixture 0.4MPa
Reductase 12 h, obtains 20wt%Ni-Al2O3Catalyst.Reaction temperature is down to after reduction, for being catalyzed diethylene glycol (DEG) and tert-butylamine
The reaction of TBEE is produced in amination.It reacts and gas circuit is switched to hydrogen, reaction pressure 3MPa before starting, reaction temperature is 260 DEG C,
Reaction solution is tert-butylamine and diethylene glycol (DEG) molar ratio is 2：1 mixed solution, Liquid sample introduction amount are 1mL/h, react 6h, and DEG's turns
The yield that the selectivity that rate is 46.4%, TBEE is 1.3%, TBEE is 0.6%.Compared with catalyst prepared by infusion process,
It is substantially reduced using TBEE selectivity on the catalyst of coprecipitation preparation and yield.
Embodiment 14
Ammonium hydroxide does precipitating reagent, and aluminum nitrate is silicon source, at room temperature stir while be titrated to respectively with ammonium hydroxide pH=5,7,9,
11, continue to stir 2h, 12h is then placed under 85 DEG C of water bath conditions, 100 DEG C of baking ovens 18h, 600 DEG C of roasting 4h obtain Al2O3Point
Al is not denoted as it2O3-pH5、Al2O3-pH7、Al2O3-pH9、Al2O3-pH11.Weigh 1.14g Ni (NO3)2·6H2O adds distilled water
Nickel salt solution is impregnated in the made Al of 2g 40-60 mesh by 1.6mL, stirring and dissolving respectively2O3-pH5、Al2O3-pH7、Al2O3-pH9、
Al2O3On-pH11 carrier, it is then placed on 80 DEG C of water-baths and dries, be placed in 100 DEG C of oven overnights, in Muffle furnace air gas
The lower 300 DEG C of roastings 1h of atmosphere, obtains 10wt%Ni/Al2O3Catalyst precursor.Take the bodies such as 1.5mL catalyst precursor and diamond dust
Product mixing, is placed in fixed bed reactors, at 500 DEG C, 10% (volume fraction) H20.5h is restored under/Ar gaseous mixture 0.4MPa,
Catalyst is obtained, is denoted as 10wt%Ni/Al respectively2O3- pH5,10wt%Ni/Al2O3- pH7,10wt%Ni/Al2O3-pH9、
10wt%Ni/Al2O3-pH11.It is down to reaction temperature after reduction, produces TBEE for being catalyzed diethylene glycol (DEG) and tert-butylamine amination
Reaction.It reacts and gas circuit is switched to hydrogen, reaction pressure 2MPa before starting, reaction temperature is 250 DEG C, and reaction solution is tertiary fourth
Amine and diethylene glycol (DEG) molar ratio are 2：1 mixed solution, Liquid sample introduction amount are 6mL/h, react 6h, reaction evaluating result such as table 2：
Table 2：Diethylene glycol (DEG) and tert-butylamine aminating reaction performance evaluation on the carrier loaded Raney nickel of condition of different pH preparation
As a result
Embodiment 15
Ammonium hydroxide makees precipitating reagent, and aluminum nitrate is silicon source, with ammonia water titration to pH=9 while stirring at room temperature, continues to stir
2h, then places 12h under 85 DEG C of water bath conditions, and 100 DEG C of baking ovens 18h, 600 DEG C of roasting 4h obtain Al2O3.Weigh 1.14g Ni
(NO3)2·6H2O, adds distilled water 1.6mL, and stirring and dissolving is impregnated in the made Al of 2g 40-60 mesh using equi-volume impregnating2O3It carries
On body, it is then placed on 80 DEG C of water-baths and dries, be placed in 100 DEG C of oven overnights, 300 DEG C of roastings under air atmosphere in Muffle furnace
1h is burnt, 10wt%Ni/Al is obtained2O3Catalyst precursor.It takes 1.5mL catalyst precursor to mix in equal volume with diamond dust, is placed in
In fixed bed reactors, at 500 DEG C, 10% (volume fraction) H20.5h is restored under/Ar gaseous mixture 0.4MPa, obtains 10wt%
Ni/Al2O3Catalyst.It is down to reaction temperature after reduction, produces the anti-of TBEE with tert-butylamine amination for being catalyzed diethylene glycol (DEG)
It answers.It reacts and gas circuit is switched to hydrogen before starting, reaction pressure is respectively set as 1MPa, 2MPa, 3MPa, reaction temperature 250
DEG C, reaction solution is tert-butylamine and diethylene glycol (DEG) molar ratio is 2：1 mixed solution, Liquid sample introduction amount are 6mL/h, react 6h, reaction
Evaluation result such as table 3：
Table 3：Diethylene glycol (DEG) and tert-butylamine aminating reaction Evaluation results when reaction pressure difference
| Reaction pressure (MPa) | DEG conversion ratio (%) | TBEE selectivity (%) | TBEE yield (%) |
| 1 | 45.7 | 18.6 | 8.5 |
| 2 | 68.6 | 6.3 | 4.3 |
| 3 | 67.5 | 1.7 | 1.1 |
Embodiment 16
Ammonium hydroxide does precipitating reagent, and aluminum nitrate is silicon source, with ammonia water titration to pH=9 while stirring at room temperature, continues to stir
2h, then places 12h under 85 DEG C of water bath conditions, and 100 DEG C of baking ovens 18h, 600 DEG C of roasting 4h obtain Al2O3.Weigh 1.14g Ni
(NO3)2·6H2O, adds distilled water 1.6mL, and stirring and dissolving is impregnated in the made Al of 2g 40-60 mesh using equi-volume impregnating2O3It carries
On body, it is then placed on 80 DEG C of water-baths and dries, be placed in 100 DEG C of oven overnights, 300 DEG C of roastings under air atmosphere in Muffle furnace
1h is burnt, 10wt%Ni/Al is obtained2O3Catalyst precursor takes catalyst precursor powder 0.25g in quartz ampoule, and 500 DEG C,
10% (volume fraction) H20.5h is restored under/Ar gaseous mixture 0.4MPa, obtains 10wt%Ni/Al2O3Catalyst.After reduction
It is down to room temperature, produces reacting for TBEE with tert-butylamine amination for being catalyzed diethylene glycol (DEG) in batch tank reactor.
Reacting addition tert-butylamine and diethylene glycol (DEG) molar ratio in forward reaction kettle is 2：1 mixed solution, adds catalyst,
Adjusting Hydrogen Vapor Pressure is 0.5Mpa, and reaction temperature is respectively 200 DEG C, 230 DEG C, 250 DEG C, reacts 8h, reaction evaluating result such as table
4：
Table 4：Diethylene glycol (DEG) and tert-butylamine aminating reaction Evaluation results when reaction temperature difference
| Reaction temperature (DEG C) | DEG conversion ratio (%) | TBEE selectivity (%) | TBEE yield (%) |
| 200 | 41.1 | 77.3 | 31.8 |
| 230 | 93.0 | 58.4 | 54.3 |
| 250 | 92.2 | 21.0 | 19.4 |
Nickel-base catalyst, which produces reacting for TBEE with tert-butylamine amination condensation to diethylene glycol (DEG), has certain catalytic performance, choosing
Different reaction units, carrier and reaction condition are selected, reactivity and selectivity have apparent difference.In batch tank reactor
The reactivity of catalyst is significantly higher, there is the selectivity of TBEE and the stability of reaction bright catalyst in fixed bed reactors
It is aobvious to improve.
Claims (8)
1. a kind of nickel-base catalyst, it is characterised in that：It is prepared by following steps,
1) nickel salt is dissolved in distilled water, stirring to dissolution, nickel salt concentration range 5 × 10-4~5.0moL/L；
2) on nickel salt solution incipient impregnation to 1~3g carrier 0.5 will be impregnated~for 24 hours, the pore volume of carrier and nickel salt solution
Volume is identical；
3) sample for obtaining step 2) is placed under 50~85 DEG C of water bath conditions and is evaporated, and then dries under the conditions of 100~120 DEG C
2~for 24 hours；
4) sample obtained after step 3) drying is roasted under 250~650 DEG C of air atmospheres 0.5~8h, is made described Ni-based
Catalyst precursor；
5) by the resulting nickel-base catalyst presoma of step 4) in H2Under the conditions of/Ar gaseous mixture, 300~600 DEG C of 0.5~8h of reduction,
Obtain nickel-base catalyst.
2. a kind of nickel-base catalyst as described in claim 1, it is characterised in that：In nickel-base catalyst, nickel salt load capacity be 2~
50wt%.
3. a kind of nickel-base catalyst as described in claim 1, it is characterised in that：Carrier is SiO2、Al2O3、TiO2, MgO, activity
One of charcoal, MCM-22, MCM-41, ZSM-5, SBA-15,6201 carriers or 102 carriers.
4. a kind of nickel-base catalyst as described in claim 1, it is characterised in that：Step 5) is carried out in fixed bed reactors
The nickel-base catalyst presoma that mixes in equal volume with diamond dust is added in fixed bed reactors flat-temperature zone in reduction, reactor its
Diamond dust is filled in remaining part position, in 300~600 DEG C, H20.5~8h of in-situ reducing under the conditions of/Ar gaseous mixture, is cooled to 180~300
DEG C, obtain nickel-base catalyst；H2Percentage by volume 8~15%.
5. a kind of nickel-base catalyst as described in claim 1, it is characterised in that：Step 5) is carried out in batch tank reactor
Reduction, that is, take nickel-base catalyst presoma in quartz ampoule, in 300~600 DEG C, H2Under the conditions of/Ar gaseous mixture reduction 0.5~
8h is down to room temperature after reduction, obtains nickel-base catalyst；H2Percentage by volume 8~15%.
6. nickel-base catalyst described in claim 1 prepares the tertiary fourth of serious sterically hindered amines in catalysis tert-butylamine and diethylene glycol (DEG) amination
Application in aminoethoxy ethyl alcohol.
7. nickel-base catalyst as claimed in claim 6 prepares serious sterically hindered amines uncle in catalysis tert-butylamine and diethylene glycol (DEG) amination
Application in butylamine base oxethyl ethyl alcohol, it is characterised in that：In fixed bed reactors, by 1.5mL catalyst and diamond dust etc.
Under volume mixture, reaction temperature is 180~300 DEG C, and reaction solution is tert-butylamine and diethylene glycol (DEG) molar ratio is 0.5~10：1 mixing
Solution, Liquid sample introduction amount are 0.5~20mL/h, and switching reducing atmosphere is reaction atmosphere before reacting, and pressure is 0.5~5MPa.
8. nickel-base catalyst as claimed in claim 6 prepares the tertiary fourth of serious sterically hindered amines in catalysis tert-butylamine and diethylene glycol (DEG) amination
Application in aminoethoxy ethyl alcohol, it is characterised in that：In batch tank reactor, reaction solution is that tert-butylamine rubs with diethylene glycol (DEG)
You are than being 0.5~10：1 mixed solution, catalyst amount are 1~2wt% of reaction mixture, and reaction temperature is 180~300
DEG C, adjusting Hydrogen Vapor Pressure is 0.5~3MPa.
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| CN117417262A (en) * | 2023-10-19 | 2024-01-19 | 山东达民化工股份有限公司 | Preparation method of diglycolamine |
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