CN109201105A - A kind of preparation method of deep desulfurization catalyst - Google Patents
A kind of preparation method of deep desulfurization catalyst Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
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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
- B01J27/188—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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- 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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- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/163—X-type faujasite
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/14—After treatment, characterised by the effect to be obtained to alter the inside of the molecular sieve channels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/37—Acid treatment
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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
- C10G2300/207—Acid gases, e.g. H2S, COS, SO2, HCN
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Abstract
The present invention relates to one kind to be used for fuel oil catalysis oxidation deep desulfuration, prepare the catalyst in ultra-clean fuel oil field, utilize modified molecular sieve carried heteropoly acid, it is prepared into support type desulphurization catalyst, keep heteropoly acid high activity, it is highly selective while, improve the repeat performance of heteropoly acid.One aspect of the present invention utilizes strong acid and strong oxidizer pretreatment molecular sieves, is then modified using ion exchange to molecular sieve, and local location in molecular sieve pore passage is made to improve electrostatic field intensity, is polarized sulfide molecules to be easy to be adsorbed and then be catalyzed；On the other hand it selects heteropoly acid for major catalyst, greatly improves molecular sieve to the catalytic performance of organic sulfur compound.Because should be after catalyst is applied to production, desulfurization degree height be improved, production cost and operating cost are greatly lowered.
Description
Technical field
The present invention relates to one kind to be used for fuel oil catalysis oxidation deep desulfuration, prepares the catalysis of ultra-clean fuel oil
Agent.
Background technique
What is be industrially widely used at present is fuel oil hydrodesulfurization technology, can remove the vulcanization such as mercaptan, thioether, thiophene
Object, but deep desulfuration operating condition is harsher, and hydrogen-consuming volume is big, operation equipment valuableness, especially dibenzothiophenes class
Sulfide hydrodesulfurization difficulty is bigger.Non- hydrodesulfurization operating condition is milder, and technological equipment investment and operating cost are low, ring
Border pollution is few, especially catalytic oxidation desulfurization technology, good to the removal effect of intractable benzothiophene and its derivative, by
To the extensive concern of researchers at home and abroad.The key of catalytic oxidation desulfurization is high activity, highly selective, high reusability
Catalyst.The catalyst such as metal salt, metal oxide and organic acid are used equally for catalytic oxidation desulfurization, but oxidant disappears in the process
Consumption is larger, and desulfurization effect is also undesirable.Heteropoly acid has unique six sides cage structure as superpower solid acid catalyst,
Unique acid, multi-functional and " false liquid phase " behavior, different elements can express acid and oxidation-reduction quality difference, make
Its catalytic performance is controllable, is conducive to Catalyst Design, is widely used in catalytic field.But heteropolyacid catalyst makes
Difficult, the serious problem of catalyst loss is recycled with existing in the process.Carried heteropoly acid catalyst is developed to deep desulfuration skill
Art development is of great significance.
Desulfurization effect and catalyst reusability can be improved in carried heteropoly acid catalyst large specific surface area, avoids miscellaneous
The shortcomings that largely being lost in the use process of polyacid.
Summary of the invention
It is mentioned the purpose of the present invention is keeping the high activity, highly selective of heteropoly acid, while using molecular sieve carried method
The repeat performance of high heteropoly acid reduces catalyst loss.
The purpose of the present invention is being realized by following scheme, preparation step is as follows:
(1) molecular sieve is obtained as catalyst carrier by carrying out the modified pretreatment in surface to 13X or ZSM-5 molecular sieve,
Modification includes using strong acid (sulfuric acid, hydrochloric acid or nitric acid) and strong oxidizer (ozone or hydrogen peroxide) impregnation molecular sieve,
Strong acid and strong oxidizer volume ratio are 1:5~5:1, to improve molecular sieve surface performance；Then reuse rare earth ion or
The solution of transition metal ions carries out incipient impregnation to pretreated molecular sieve, and progress ion exchange obtains molecular sieve supported
Body, the rare earth ion or transition metal ions concentration are 0.05mol/L~0.8mol/L.
(2) above-mentioned molecular sieve carrier 2g is taken, it is 2 hours dry at 400 DEG C, it is added in reactor after cooling, and wherein
60mL toluene and 0.1mL~5mL silane coupling agent is added, flows back 1h~10h hours, after cooling, with a large amount of ethanol washings three
It after secondary, is dried under reduced pressure at 100 DEG C 3 hours, the silane coupling agent is 3- aminopropyl triethoxysilane, 3- (metering system
Acyl chlorides) propyl front three oxosilane, KH-540, KH550, KH560, KH 580, one of KH590.
(3) product, 40mL isopropanol and 0.5g~5g heteropoly acid that step (2) obtain are added in reactor, reflux 2 is small
When, after cooling, washed three times with a large amount of isopropanols, after washing, be dried under reduced pressure in 100 DEG C 5 hours, catalysis is prepared
Agent, the heteropoly acid are one or both of phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid, P-Mo-Wo acid, silicon molybdenum wolframic acid.
The present invention has the effect of deep desulfuration positive: one aspect of the present invention is utilized to be located in advance using strong acid and strong oxidizer
It manages molecular sieve and realizes ion exchange, realization is modified molecular sieve, and local location in molecular sieve pore passage is made to improve electrostatic field
Intensity is polarized sulfide molecules to be easy to be adsorbed, therefore improves the catalytic conversion efficiency to organic sulfur compound；This
On the other hand invention selects heteropoly acid for major catalyst, greatly improve molecular sieve to the catalytic performance of organic sulfur compound.Cause
Should be after catalyst be applied to production, desulfurization degree improves, production cost and operating cost are greatly lowered.
Specific embodiment
Desulfurization is carried out using following embodiment, to verify the excellent desulfurization of catalytic oxidation desulfurization catalyst of the invention
Performance.
Embodiment 1
Method for preparing catalyst is as follows:
(1) molecular sieve is obtained as catalyst carrier, modification packet by carrying out surface modification treatment to 13X molecular sieve
It includes using strong acid (sulfuric acid) and strong oxidizer (hydrogen peroxide) pretreatment molecular sieves, strong acid and strong oxidizer volume ratio are 1:1, to change
Into molecular sieve surface performance；Then the solution for reusing rare earth ion (cerous nitrate) carries out pretreated molecular sieve etc.
Volume impregnation realizes that ion exchange, the concentration of the rare earth ion are 0.1mol/L.
(2) above-mentioned molecular sieve carrier 2g is taken, it is 2 hours dry at 400 DEG C, it is added in reactor after cooling, and wherein
60mL toluene and 0.2mL silane coupling agent is added, flows back 4h hour, after cooling down, with a large amount of ethanol washings three times after, in 100
It is dried under reduced pressure at DEG C 3 hours, the silane coupling agent is 3- aminopropyl triethoxysilane.
(3) product, 40mL isopropanol and 0.2g heteropoly acid that step (2) obtain are added in reactor, flows back 2 hours,
It after cooling, is washed three times with a large amount of isopropanols, after washing, is dried under reduced pressure in 100 DEG C 5 hours, catalyst is prepared, institute
Stating heteropoly acid is phosphotungstic acid.
Desulfurization effect evaluation:
The evaluation test of desulfurizing agent carries out in intermittent desulfurizer, to contain the dibenzothiophenes of 500 μ g/g sulfur contents
N-heptane solution is simulation oil desulfurization object, takes 20mL simulation oil, is added 2.5mL hydrogen peroxide (30%), 0.05g cetyl three
Methyl bromide ammonium and 0.05 gram of desulphurization catalyst measure sulfur content after stirring 3h at 30 DEG C, and calculating desulfurization degree is 95.2%, weight
It the use of desulfurization degree after 3 times is again 90%.
Embodiment 2
Method for preparing catalyst is as follows:
(1) molecular sieve is obtained as catalyst carrier, modification packet by carrying out surface modification treatment to 13X molecular sieve
It includes using strong acid (hydrochloric acid) and strong oxidizer (hydrogen peroxide) pretreatment molecular sieves, strong acid and strong oxidizer volume ratio are 1:2, to change
Into molecular sieve surface performance；Then the solution for reusing transition metal ions (copper nitrate) carries out pretreated molecular sieve etc.
Volume impregnation realizes that ion exchange, the transition metal ions concentration are 0.2mol/L.
(2) above-mentioned molecular sieve carrier 2g is taken, it is 2 hours dry at 400 DEG C, it is added in reactor after cooling, and wherein
60mL toluene and 0.3mL silane coupling agent is added, flows back 8h hour, after cooling down, with a large amount of ethanol washings three times after, in 100
It is dried under reduced pressure at DEG C 3 hours, the silane coupling agent is KH-540.
(3) product, 40mL isopropanol and 0.3g heteropoly acid that step (2) obtain are added in reactor, flows back 2 hours,
It after cooling, is washed three times with a large amount of isopropanols, after washing, is dried under reduced pressure in 100 DEG C 5 hours, catalyst is prepared, institute
Stating heteropoly acid is phosphomolybdic acid.
Desulfurization effect evaluation:
The evaluation test of test desulfurizing agent carries out in intermittent desulfurizer, to contain the dibenzo of 500 μ g/g sulfur contents
Thiophene n-heptane solution is simulation oil desulfurization object, takes 20mL simulation oil, is added 2.5mL hydrogen peroxide (30%), 0.05 gram 16
Alkyl trimethyl ammonium bromide and 0.05 gram of desulphurization catalyst measure sulfur content after stirring 3h at 30 DEG C, calculate desulfurization degree and are
97.1%, desulfurization degree is 92.1% after reusing 3 times.
Embodiment 3:
Method for preparing catalyst is as follows:
(1) molecular sieve is obtained as catalyst carrier, modification by carrying out surface modification treatment to ZSM-5 molecular sieve
Including using strong acid (hydrochloric acid) and strong oxidizer (hydrogen peroxide) pretreatment molecular sieves, strong acid and strong oxidizer volume ratio are 1:1, with
Improve molecular sieve surface performance；Then the solution for reusing transition metal ions (cobalt nitrate) carries out pretreated molecular sieve
Incipient impregnation realizes that ion exchange, the rare earth ion or transition metal ions concentration are 0.1mol/L.
(2) above-mentioned molecular sieve carrier 2g is taken, it is 2 hours dry at 400 DEG C, it is added in reactor after cooling, and wherein
60mL toluene and 0.4mL silane coupling agent is added, flows back 6h hour, after cooling down, with a large amount of ethanol washings three times after, in 100
It is dried under reduced pressure at DEG C 3 hours, the silane coupling agent is KH560.
(3) product, 40mL isopropanol and 0.4g heteropoly acid that step (2) obtain are added in reactor, flows back 2 hours,
It after cooling, is washed three times with a large amount of isopropanols, after washing, is dried under reduced pressure in 100 DEG C 5 hours, catalyst is prepared, institute
Stating heteropoly acid is P-Mo-Wo acid.
Desulfurization effect evaluation:
The evaluation test of test desulfurizing agent carries out in intermittent desulfurizer, to contain the dibenzo of 500 μ g/g sulfur contents
The gasoline of thiophene is desulfurization object, takes 20mL gasoline, is added 2.5mL hydrogen peroxide (30%), 0.05 gram of cetyl trimethyl bromine
Change ammonium and above-mentioned 0.03 gram of desulphurization catalyst, measure sulfur content after 3h is stirred at 30 DEG C, calculating desulfurization degree is 90.2%, weight
It the use of desulfurization degree after 3 times is again 88.2%.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (5)
1. a kind of preparation method for fuel oil catalysis oxidation deep desulfurization catalyst, preparation step are as follows:
(1) molecular sieve is obtained as catalyst carrier, at modification by carrying out surface modification treatment to 13X or ZSM-5 molecular sieve
Reason include use strong acid (sulfuric acid, hydrochloric acid or nitric acid) and strong oxidizer (ozone or hydrogen peroxide) impregnation molecular sieve, strong acid with
Strong oxidizer volume ratio is 1:5~5:1, to improve molecular sieve surface performance, then reuses rare earth ion or transition gold
The solution for belonging to ion carries out ion exchange to pretreated molecular sieve and obtains molecular sieve carrier；
(2) the molecular sieve carrier 2g for taking above-mentioned steps (1), it is 2 hours dry at 400 DEG C, it is added in reactor after cooling, and
60mL toluene and 0.1mL~5mL silane coupling agent is wherein added, flows back 1h~10h hours, after cooling, is washed with a large amount of ethyl alcohol
It washs three times, is dried under reduced pressure at 100 DEG C 3 hours；
(3) product, 40mL isopropanol and 0.5g~5g heteropoly acid that step (2) obtain are added in reactor, flows back 2 hours,
It after cooling, is washed three times with a large amount of isopropanols, after washing, is dried under reduced pressure in 100 DEG C 5 hours, catalyst is prepared.
2. the preparation method of desulphurization catalyst according to claim 1, it is characterised in that step (1) institute in claim 1
The ion exchange stated is to carry out ion exchange using incipient impregnation method.
3. the preparation method of desulphurization catalyst according to claim 1, it is characterised in that step (1) institute in claim 1
The rare earth ion or transition metal ions concentration stated are 0.05mol/L~0.8mol/L.
4. the preparation method of desulphurization catalyst according to claim 1, it is characterised in that step (2) institute in claim 1
The silane coupling agent stated be 3- aminopropyl triethoxysilane, 3- (methacrylic chloride) propyl front three oxosilane, KH-540,
One of KH550, KH560, KH 580, KH590.
5. the preparation method of desulphurization catalyst according to claim 1, it is characterised in that step (3) institute in claim 1
The heteropoly acid stated is one or both of phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid, P-Mo-Wo acid, silicon molybdenum wolframic acid.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113174036A (en) * | 2021-04-28 | 2021-07-27 | 浙江联盛化学股份有限公司 | Rare earth doped molecular sieve catalyst, preparation method and application thereof |
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| CN102357366A (en) * | 2011-09-02 | 2012-02-22 | 新疆大学 | Non-mercury catalyst used for acetylene hydrochlorination |
| CN107413293A (en) * | 2017-08-09 | 2017-12-01 | 沈阳三聚凯特催化剂有限公司 | A kind of desulfurizing agent and preparation method and application |
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2018
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Patent Citations (4)
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| US20060211906A1 (en) * | 2003-03-28 | 2006-09-21 | Berezutskiy Vladimir M | Method for purifying a liquid medium |
| CN102134508A (en) * | 2011-01-30 | 2011-07-27 | 山东大学 | Oxidation desulfuration method based on modified MCM-41 anchored heteropolyacid catalyst |
| CN102357366A (en) * | 2011-09-02 | 2012-02-22 | 新疆大学 | Non-mercury catalyst used for acetylene hydrochlorination |
| CN107413293A (en) * | 2017-08-09 | 2017-12-01 | 沈阳三聚凯特催化剂有限公司 | A kind of desulfurizing agent and preparation method and application |
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| ROGHAYE DEHGHAN ET AL.: "Zeolites for adsorptive desulfurization from fuels", 《ELSEVIER》 * |
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| 李淑培: "《石油加工工艺学 中册》", 31 October 1991, 中国石化出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113174036A (en) * | 2021-04-28 | 2021-07-27 | 浙江联盛化学股份有限公司 | Rare earth doped molecular sieve catalyst, preparation method and application thereof |
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