CN108295879A - A kind of polyamidoamine dendrimer fixes the preparation method and application of heteropolyacid catalyst - Google Patents
A kind of polyamidoamine dendrimer fixes the preparation method and application of heteropolyacid catalyst Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/003—Dendrimers
- C08G83/004—After treatment of dendrimers
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
- C10G27/12—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen with oxygen-generating compounds, e.g. per-compounds, chromic acid, chromates
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
The invention belongs to the deep processing of petrochemical industry oil product and green technology crossing domains, and in particular to a kind of preparation method that daiamid type dendrimer fixes heteropolyacid catalyst and its application in oxidation sweetening.Daiamid type dendrimer is add to deionized water, heating stirring；Heteropoly acid is dissolved in wiring solution-forming in deionized water and above-mentioned daiamid type dendrimer solution is added dropwise, temperature is controlled, is vigorously stirred, dialysis separation is made daiamid type dendrimer and fixes heteropolyacid catalyst.Catalyst made from the method for the present invention is used for oxidation sweetening, and compared with traditional catalyst, desulfurization condition is mild, and can the desulfurization in hydrogen peroxide (0.5% 5%) system of low concentration, the resolution ratio of hydrogen peroxide is low, and desulfurization effect is good in oil product.
Description
Technical field
The invention belongs to petrochemical industry oil product deep processing industry and green technology crossing domains, and in particular to a kind of polyamides
The preparation method and its application in oxidation sweetening that amine-amine type dendrimer fixes heteropolyacid catalyst.
Background technology
In recent years, growing energy demand, further serious environmental problem so that the refinement of crude oil is faced with huge
Challenge.Fuel oil accounts for 34.5% as a kind of traditional energy in world's energy resource structure, it is contemplated that from 2015 to 2035 year,
The world increases (OPEC2011) demand of fuel oil with 8% speed every year on average.But the tail gas pair generated after fuel oil burning
The harm of human body and environment also getting worse.Major pollutants in tail gas have oxysulfide (SOx), nitrogen oxides, one oxidation
Carbon, hydrocarbon and solid particulate contaminant etc..Sulfur content influences the discharge of exhaust pollutant very big, vulcanization in fuel oil
After closing object burning, the sour gas such as a large amount of SOx are on the one hand generated, form acid rain and sour gas pollution；On the other hand, sulphur pair
Solid particulate matter is obviously promoted effect.Therefore, the low-sulfur of fuel oil by countries in the world common concern.From
From the point of view of the European and American countries fuel environment protection regulation of appearance, it is to produce the critical issue of clean fuel oil to reduce the sulfur content in fuel oil.
Currently, the desulfurization technology industrially used is mainly hydrodesulfurization, which needs high temperature, high pressure, hydrogen atmosphere
Equal exacting terms.Therefore, in order to reduce fuel cost, other sulfur removal technologies are such as：Oxidation sweetening, abstraction desulfurization adsorb desulfurization,
Biological desulphurization comes into being.Wherein, oxidation sweetening is since low energy consumption is considered as one of most promising desulfurization technology.It is former
It is corresponding sulfoxide or sulfone substance that reason, which is by selective oxidation of sulfur containing compounds in particular such as thiophenic sulfurs in fuel oil, since oxidation product has
Higher polarity, it is possible to be extracted them by polar solvent, to achieve the purpose that desulfurization.In order to improve oxidation
The desulphurizing ability of desulfurization and the selectivity for improving oxidation sweetening introduce various catalyst structure catalysis oxygen in oxidation sweetening system
It is one of effective method to change desulfurization system.
The oxidant species that oxidative desulfurization techniques are related to are more, and leading position is in by oxidant of hydrogen peroxide.H2O2It is rotten
Corrosion is low, and byproduct of reaction is water and oxygen, has been inherently eliminated the pollution sources of oxidation process, non-environmental-pollution.Heteropoly acid
As a kind of novel catalysis material, there is the advantages that composition is simple, structure determination, component is easily adjusted, studied by catalytic field
The extensive concern of person, as catalyst depth oxidation sweetening there are many research report.But the surface area because of heteropoly acid and hole
Gap rate is relatively low, and active site is embedded, and catalytic oxidation desulfurization effect is poor, it is therefore desirable to which it is fixed.As silica,
The inorganic matters such as activated carbon, titanium dioxide fix heteropoly acid catalysis desulfurization also it has been reported that still inorganic matter fixes heteropoly acid and oil
Phase poor compatibility causes oxidation sweetening effect also poor.Therefore, it finds new catalysis material, explore new catalyst cured skill
Art is the emphasis of current research work.
Invention content
In order to which the surface area and porosity that solve heteropoly acid oxidation sweetening existing in the prior art are relatively low, inorganic matter is fixed
Heteropoly acid and oil phase poor compatibility lead to oxidation sweetening effect also poor technical problem.
The present invention provides a kind of polyamidoamine dendrimer fix heteropolyacid catalyst preparation method and its
For the method for oxidation sweetening, catalyst produced by the present invention is used for oxidation sweetening, and reaction condition is mild, easy to operate, can have
Sulfide in the removing oil product of effect.
The present invention is achieved by the following technical solutions：
Polyamidoamine dendrimer of the present invention fixes the preparation method of heteropolyacid catalyst, concrete technology step
Suddenly it is：
(1) the polyamidoamine dendrimer of 1.0g-2.0g is added in the deionized water of 10ml-200ml,
1-10h is stirred, the temperature in whipping process is controlled at 10-80 DEG C, is stirred 1-10h, is obtained polyamidoamine dendrimer
Solution；
(2) 1.0g-10.0g heteropoly acids are dissolved in the deionized water of 20ml-50ml and are made into heteropoly acid solution；
(3) by the polyamidoamine dendrimer solution that step (1) obtains be added drop-wise to step (2) obtain it is miscellaneous more
In acid solution, temperature is controlled at 20-60 DEG C during dropwise addition, is vigorously stirred 1-10h, dialysis separation, polyamide-amide and heteropoly acid
Polyamidoamine dendrimer fixation heteropoly acid has been made by being condensed acylation reaction.
Wherein, the polyamidoamine dendrimer is prepared by the following preparation method：Utilize acrylate
Michael additions are carried out with ammonia or ethylenediamine, then carrying out amine exchange reaction with excessive diamines and ester obtains amide.
Michael addition reactions and amidation process alternately obtain polyamide-amide dendrimer.It often carries out primary complete
Michael addition reactions and amidation condensation reaction, polyamide-amide dendrimer be just extended to high one layer of molecule
Generation.Polyamidoamine dendrimer algebraically of the present invention is 0-10 generations, and structure is as follows：
The heteropoly acid is H3PW12O40、H3PMo12O40、H4SiW12O40、H4PMo11V1O40、H5PMo10V2O40Or
H6PMo9V3O40In any one.
The present invention also provides the applications that a kind of polyamidoamine dendrimer fixes heteropolyacid catalyst, this is urged
Agent is used for catalytic oxidation desulfurization, and the method for catalytic oxidation desulfurization includes the following steps：
(1) oxidant H is taken2O2Heteropoly acid is fixed with catalyst polyamidoamine dendrimer, premixing obtains oxygen
The mixture of agent and catalyst.It is spare；
(2) according to volume ratio it is (1-50) by pending oil product and acetonitrile under normal temperature and pressure conditions：1 ratio mixing, control
20-90 DEG C of reaction temperature processed is added the mixture of oxidant and catalyst made from step (1), reacts 1-6h under stirring condition.
Wherein, it is pending oil quality that polyamidoamine dendrimer, which fixes heteropolyacid catalyst dosage,
0.1-10%, H2O2Dosage calculate in the following manner：H is determined with the molal quantity of sulphur (S) in pending oil product2O2Molal quantity,
O/S molar ratios are (1-20)：1.
The pending oil product includes the semi-finished product oil in crude oil, fuel oil and crude refinement processes.
The present invention is based on the oxidation desulfurizing method that polyamidoamine dendrimer fixes heteropolyacid catalyst, reactions
Mild condition, it is easy to operate, it can effectively remove the sulfide in oil product.
The beneficial effects of the invention are as follows：The present invention has synthesized a kind of gathering with covalent bond structure by being condensed acylation reaction
Amide-amine type dendrimer fixes heteropolyacid catalyst.The preparation process of the catalyst is simple, using water as solvent, in temperature
It is synthesized under the temperature condition of sum.Specific surface area of catalyst made from the method for the present invention is big, with oil product and acetonitrile all have compared with
Good compatibility, during oxidation sweetening, using catalysis oxidation in the principle removing oil product that extraction and separation are combined
Sulfur-containing compound, surface area and the porosity for solving heteropoly acid oxidation sweetening are relatively low, and inorganic matter fixes heteropoly acid and oil phase phase
Capacitive is poor, the technical problem for causing oxidation sweetening effect poor.Catalyst obtained is fixed for oxidation sweetening with inorganic material
Heteropoly acid is compared, and desulfurization benefit significantly improves, and is a kind of production technology efficiently, economic, environmentally friendly.
Specific implementation mode
With reference to embodiment, the present invention is further illustrated, but should be noted that the present invention is not limited under
Embodiment is stated, without departing from the purpose of the present invention, all changes implementation is included in protection scope of the present invention.
Embodiment 1
Polyamidoamine dendrimer/H3PW12O40Preparation：
The polyamidoamine dendrimer (algebraically 1) of 2g is added in the deionized water of 50ml, 2h is stirred,
Temperature is 30 DEG C；By 3g heteropoly acids (H3PW12O40) it is dissolved in wiring solution-forming in the deionized water of 30ml, and above-mentioned polyamides is added dropwise
Amine-amine type dendrimer solution, temperature are controlled at 30 DEG C, are vigorously stirred 2h, and polyamidoamine tree is made in dialysis separation
Dendritic macromolecule fixes heteropolyacid catalyst.
Embodiment 2
Polyamidoamine dendrimer/H3PMo12O40Preparation：
The polyamidoamine dendrimer (algebraically 2) of 1.5g is added in the deionized water of 40ml, is stirred
3h, temperature are 40 DEG C；By 2g heteropoly acids (H3PMo12O40) it is dissolved in wiring solution-forming in the deionized water of 20ml, and be added dropwise above-mentioned poly-
Amide-amine type dendrimer solution, temperature are controlled at 50 DEG C, are vigorously stirred 3h, and polyamidoamine is made in dialysis separation
Dendrimer fixes heteropolyacid catalyst.
Embodiment 3
Polyamidoamine dendrimer/H4SiW12O40Preparation：
The polyamidoamine dendrimer (algebraically 3) of 1.5g is added in the deionized water of 40ml, is stirred
3h, temperature are 40 DEG C；By 2g heteropoly acids (H4SiW12O40) it is dissolved in wiring solution-forming in the deionized water of 20ml, and be added dropwise above-mentioned poly-
Amide-amine type dendrimer solution, temperature are controlled at 50 DEG C, are vigorously stirred 4h, and polyamidoamine is made in dialysis separation
Dendrimer fixes heteropolyacid catalyst.
Embodiment 4
Polyamidoamine dendrimer/H6PMo9V3O40Preparation：
The polyamidoamine dendrimer (algebraically 3) of 1.5g is added in the deionized water of 40ml, is stirred
3h, temperature are 40 DEG C；By 2g heteropoly acids (H6PMo9V3O40) it is dissolved in wiring solution-forming in the deionized water of 20ml, and be added dropwise above-mentioned
Polyamidoamine dendrimer solution, temperature are controlled at 50 DEG C, are vigorously stirred 2h, and polyamide-amide is made in dialysis separation
Type dendrimer fixes heteropolyacid catalyst.
Embodiment 5
Polyamidoamine dendrimer/H4PMo11V1O40Preparation：
The polyamidoamine dendrimer (algebraically 3) of 1.5g is added in the deionized water of 40ml, is stirred
6h, temperature are 20 DEG C；By 2g heteropoly acids (H4PMo11V1O40) it is dissolved in wiring solution-forming in the deionized water of 20ml, and be added dropwise above-mentioned
Polyamidoamine dendrimer solution, temperature are controlled at 70 DEG C, are vigorously stirred 2h, and polyamide-amide is made in dialysis separation
Type dendrimer fixes heteropolyacid catalyst.
Embodiment 6
The desulfurization effect of the simulation oil of dibenzothiophenes (DBT)-normal octane
It is to represent object with the dibenzothiophenes of more difficult removing in hydrodesulfurization, a certain amount of DBT is dissolved in the just pungent of 80ml
Alkane is configured to the simulated system that sulfur content is 500ppm, 40ml acetonitriles is added, and magnetic agitation is heated to 60 DEG C, by O/S (mole
Than)=10 calculate H2O2Addition fixes H by 1% normal octane Mass Calculation polyamidoamine dendrimer3PW12O40It urges
Agent addition, by H2O2With the immobilized H of polyamidoamine dendrimer3PW12O40Catalyst is added to above-mentioned analogue body
System, after reacting 3h, the conversion ratio of DBT reaches 95.2% in normal octane.
Embodiment 7
The desulfurization effect of the simulation oil of dibenzothiophenes (DBT) -92# gasoline
It is to represent object with the dibenzothiophenes of more difficult removing in hydrodesulfurization, a certain amount of DBT is dissolved in the 92# vapour of 80ml
Oil is configured to the simulated system that sulfur content is 500ppm, 60ml acetonitriles is added, and magnetic agitation is heated to 40 DEG C, by O/S (mole
Than)=15 calculate H2O2Addition calculates polyamidoamine dendrimer/H by 1%92# quality of gasolines3PMo12O40It urges
Agent addition, by H2O2H is fixed with polyamidoamine dendrimer3PMo12O40Catalyst is added to above-mentioned analogue body
System, after reacting 5h, the conversion ratio of DBT reaches 94.8% in 92# gasoline.
Embodiment 8
The desulfurization effect of the simulation oil of dibenzothiophenes (DBT) -95# gasoline
It is to represent object with the dibenzothiophenes of more difficult removing in hydrodesulfurization, a certain amount of DBT is dissolved in the 95# vapour of 80ml
Oil is configured to the simulated system that sulfur content is 500ppm, 80ml acetonitriles is added, and magnetic agitation is heated to 40 DEG C, by O/S (mole
Than)=15 calculate H2O2Addition calculates polyamidoamine dendrimer by 1%95# quality of gasolines and fixes
H4PMo11V1O40Catalyst charge, by H2O2With the immobilized H of polyamidoamine dendrimer4PMo11V1O40Catalyst is added
To above-mentioned simulated system, after reacting 5h, the conversion ratio of DBT reaches 93.2% in 95# gasoline.
Embodiment 9
The desulfurization effect of the simulation oil of dibenzothiophenes (DBT) -92# gasoline
It is to represent object with the dibenzothiophenes of more difficult removing in hydrodesulfurization, a certain amount of DBT is dissolved in the 92# vapour of 80ml
Oil is configured to the simulated system that sulfur content is 500ppm, 60ml acetonitriles is added, and magnetic agitation is heated to 40 DEG C, by O/S (mole
Than)=15 calculate H2O2Addition calculates polyamidoamine dendrimer/H by 1%92# quality of gasolines4SiW12O40It urges
Agent addition, by H2O2H is fixed with polyamidoamine dendrimer4SiW12O40Catalyst is added to above-mentioned analogue body
System, after reacting 5h, the conversion ratio of DBT reaches 92.8% in 92# gasoline.
Embodiment 10
The desulfurization effect of the simulation oil of dibenzothiophenes (DBT) -92# gasoline
It is to represent object with the dibenzothiophenes of more difficult removing in hydrodesulfurization, a certain amount of DBT is dissolved in the 92# vapour of 80ml
Oil is configured to the simulated system that sulfur content is 500ppm, 60ml acetonitriles is added, and magnetic agitation is heated to 40 DEG C, by O/S (mole
Than)=15 calculate H2O2Addition calculates polyamidoamine dendrimer/H by 1%92# quality of gasolines6PMo9V3O40It urges
Agent addition, by H2O2H is fixed with polyamidoamine dendrimer6PMo9V3O40Catalyst is added to above-mentioned analogue body
System, after reacting 5h, the conversion ratio of DBT reaches 93.6% in 92# gasoline.
Comparative example 1
The desulfurization effect of the simulation oil of dibenzothiophenes (DBT)-normal octane compares
It is to represent object with the dibenzothiophenes of more difficult removing in hydrodesulfurization, a certain amount of DBT is dissolved in the just pungent of 80ml
Alkane is configured to the simulated system that sulfur content is 500ppm, 40ml acetonitriles is added, and magnetic agitation is heated to 60 DEG C, by O/S (mole
Than)=10 calculate H2O2Addition fixes H by 1% normal octane Mass Calculation silica3PW12O40The addition of catalyst, will
H2O2It is added to above-mentioned simulated system with catalyst, after reacting 3h, the conversion ratio of DBT reaches 88.3% in normal octane.
Comparative example 2
The desulfurization effect of the simulation oil of dibenzothiophenes (DBT) -92# gasoline
It is to represent object with the dibenzothiophenes of more difficult removing in hydrodesulfurization, a certain amount of DBT is dissolved in the 92# vapour of 80ml
Oil is configured to the simulated system that sulfur content is 500ppm, 60ml acetonitriles is added, and magnetic agitation is heated to 40 DEG C, by O/S (mole
Than)=10 calculate H2O2Addition calculates titanium dioxide by 1%92# quality of gasolines and fixes H3PW12O40The addition of catalyst,
By H2O2It is added to above-mentioned simulated system with catalyst, after reacting 3h, the conversion ratio of DBT reaches 85.1% in 92# gasoline.
Compared by each embodiment and comparative example and be can be seen that：The present invention is by being condensed having altogether for acylation reaction synthesis
The polyamidoamine dendrimer solid-carrying heteropolyacid catalyst of valence bond structure is immobilized miscellaneous for oxidation sweetening and inorganic material
Polyacid is compared, and desulfurization benefit significantly improves.
Claims (9)
1. a kind of polyamidoamine dendrimer fixes the preparation method of heteropolyacid catalyst, it is characterised in that：The system
Preparation Method is：
(1) the polyamidoamine dendrimer of 1.0g-2.0g is added in the deionized water of 10ml-200ml, is stirred
Obtain polyamidoamine dendrimer solution；
(2) 1.0g-10.0g heteropoly acids are dissolved in the deionized water of 20ml-50ml and are made into heteropoly acid solution；
(3) that the polyamidoamine dendrimer solution that step (1) obtains is added drop-wise to the heteropoly acid that step (2) obtains is molten
It in liquid, is vigorously stirred, dialysis separation is made polyamidoamine dendrimer and fixes heteropolyacid catalyst.
2. polyamidoamine dendrimer as described in claim 1 fixes the preparation method of heteropolyacid catalyst, special
Sign is：Mixing time described in step (1) is：1-10h, the temperature in whipping process are：10-80℃.
3. polyamidoamine dendrimer as described in claim 1 fixes the preparation method of heteropolyacid catalyst, special
Sign is：Step (3) be added dropwise during temperature be：20-60 DEG C, mixing time is：1-10h.
4. polyamidoamine dendrimer as described in claim 1 fixes the preparation method of heteropolyacid catalyst, special
Sign is：Polyamidoamine dendrimer described in step (1) is carried out using acrylate and ammonia or ethylenediamine
Then Michael additions carry out amine exchange reaction with excessive diamines and ester and obtain amide, Michael addition reactions and amide
Change reaction and alternately obtains polyamide-amide dendrimer.
5. polyamidoamine dendrimer as described in claim 1 fixes the preparation method of heteropolyacid catalyst, special
Sign is：Heteropoly acid described in step (2) is H3PW12O40、H3PMo12O40、H4SiW12O40、H4PMo11V1O40、H5PMo10V2O40
Or H6PMo9V3O40In one kind.
6. polyamidoamine dendrimer made from a kind of method as described in claim 1 fixes heteropolyacid catalyst
Using, it is characterised in that：The catalyst is used for catalytic oxidation desulfurization.
7. polyamidoamine dendrimer as claimed in claim 6 fixes the application of heteropolyacid catalyst, feature exists
In：The application process includes the following steps：
(1) oxidant H is taken2O2Heteropoly acid is fixed with catalyst polyamidoamine dendrimer, premixing obtains oxidant
It is spare with the mixture of catalyst；
(2) according to volume ratio it is 1-50 by pending oil product and acetonitrile under normal temperature and pressure conditions：1 ratio mixing, control reaction
20-90 DEG C of temperature is added the mixture of oxidant and catalyst made from step (1), reacts 1-6h under stirring condition.
8. polyamidoamine dendrimer as claimed in claim 7 fixes the application of heteropolyacid catalyst, feature exists
In：The polyamidoamine dendrimer fixes the 0.1-10% that heteropolyacid catalyst dosage is pending oil quality,
H2O2Dosage calculate in the following manner：H is determined with the molal quantity of sulphur (S) in pending oil product2O2Molal quantity, O/S molar ratios
For (1-20)：1.
9. polyamidoamine dendrimer as claimed in claim 7 fixes the application of heteropolyacid catalyst, feature exists
In：The pending oil product includes the semi-finished product oil in crude oil, fuel oil or crude refinement processes.
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| CN201810042313.1A CN108295879A (en) | 2018-01-17 | 2018-01-17 | A kind of polyamidoamine dendrimer fixes the preparation method and application of heteropolyacid catalyst |
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| CN201810042313.1A CN108295879A (en) | 2018-01-17 | 2018-01-17 | A kind of polyamidoamine dendrimer fixes the preparation method and application of heteropolyacid catalyst |
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| CN201810042313.1A Pending CN108295879A (en) | 2018-01-17 | 2018-01-17 | A kind of polyamidoamine dendrimer fixes the preparation method and application of heteropolyacid catalyst |
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| CN112371186A (en) * | 2020-12-15 | 2021-02-19 | 福州大学 | Preparation method of polyamine-heteropoly acid heterogeneous composite catalyst and application of polyamine-heteropoly acid heterogeneous composite catalyst in oxidative desulfurization |
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| CN112371186A (en) * | 2020-12-15 | 2021-02-19 | 福州大学 | Preparation method of polyamine-heteropoly acid heterogeneous composite catalyst and application of polyamine-heteropoly acid heterogeneous composite catalyst in oxidative desulfurization |
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