CN108126752A - A kind of phosphoric acid ester floating bed hydrogenation oil-soluble catalyst and its preparation method and application - Google Patents
A kind of phosphoric acid ester floating bed hydrogenation oil-soluble catalyst and its preparation method and application Download PDFInfo
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- CN108126752A CN108126752A CN201711137478.9A CN201711137478A CN108126752A CN 108126752 A CN108126752 A CN 108126752A CN 201711137478 A CN201711137478 A CN 201711137478A CN 108126752 A CN108126752 A CN 108126752A
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- phosphoric acid
- acid ester
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
-
- 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
- B01J27/19—Molybdenum
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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
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/64—Molybdenum
-
- 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
- C10G2300/70—Catalyst aspects
Abstract
The invention belongs to the technical fields of suspension bed hydrogenation catalyst, and in particular to a kind of phosphoric acid ester poor oil floating bed hydrogenation oil-soluble catalyst and its preparation method and application.The oil-soluble catalyst is prepared using phosphoric acid ester organic ligand and molybdenum source compound as raw material by circumfluence method, wherein, the molar ratio in phosphoric acid ester organic ligand in P elements and molybdenum source compound between molybdenum element is 1:1~1:5.Phosphoric acid ester floating bed hydrogenation oil-soluble catalyst provided by the invention, with good oil-soluble, the organo-metallic compound that can be dissolved in poor oil, organo-metallic compound can be uniformly dispersed in poor oil, it is come into full contact with poor oil and hydrogen, and its activated centre is directly generated from the thermal decomposition of catalyst, can reach very high degree of dispersion, so as to improve catalyst activity, more effectively inhibit coking.
Description
Technical field
The invention belongs to the technical fields of suspension bed hydrogenation catalyst, and in particular to a kind of phosphoric acid ester poor oil suspension bed
Hydrogenated oil soluble catalytic agent and its preparation method and application.
Background technology
It is well known that increasingly deficient, the heaviness of crude oil and in poor quality day in world wide with world energy sources resource
Become serious.At the same time, as the increasingly consumption of Coal Energy Source, the yield of coal tar are also increasing year by year in Chinese range
It is more.Currently, Chinese coal tar total output is increased with average annual 9.9% speed, the rise 16% on year-on-year basis of coal tar total output in 2016
To 20,000,000 tons.And in world wide the yield of residual oil and heavy oil the attention growing day by day for also resulting in people.Therefore effectively
Processing these poor oils is just particularly important, and Hydrofining Technology is one of most efficient solution for making poor oil lighting.
If the fuel oil and chemicals for being worth low poor oil " eat dry squeeze net " deep processing into high-quality can be made up oil product
It is insufficient, then poor oil industry can then show larger development potentiality.
Due to containing a large amount of sulphur, nitrogen, metal impurities in this kind of poor oil, and containing the charcoal for being easy to coking, and these
Impurity can cause the catalyst poisoning in processing procedure, so as to be impacted to Catalytic processes and stabilization of equipment performance, therefore right
Poor oil carries out impurity removal.This requires there is such catalyst good hydrodemetallization, hydrodesulfurization, hydrodenitrogeneration to live
Property, at the same time, also there is certain hydrogenation cracking activity.It is presently used for the catalyst master of suspension bed residual oil hydrogenation technique
Will there are three types of, be respectively：Solid powder th-1 catalyst, water-soluble catalyst, oil-soluble catalyst.And oil soluble metal catalyst is not
It only meets environmental requirement and solves the wear problem that reaction system is brought due to solid particle, and is former in weight, residual oil
It is uniformly dispersed in material, without adding emulsifier.
For this purpose, Chinese patent literature CN103980320A discloses a kind of oil-soluble molybdenum base catalyst precursor, prepare
Method is, by molybdenum source and water with 1:10~2:1 molar ratio mixing, 30~240min is reacted at 70~90 DEG C, is cooled to 30
~50 DEG C, inorganic acid is added in, is in neutrality solution；It is 3 according to the molar ratio of hydroxyl in higher alcohols and phosphorus pentasulfide:1~5:
1, higher alcohols are added in phosphorus pentasulfide, addition temperature is 50~80 DEG C, adds 5~15min of time, and higher alcohols have added
Bi Hou in the case where temperature is 70~100 DEG C, reacts 1~3h, the hydrogen sulfide gas generated in inert gas purge reaction；Then it mixes
Merging and add in acid cation exchange resin, the quality of acid cation exchange resin is 10~15% of molybdenum quality in molybdenum source,
At 70~110 DEG C, 4~8h is reacted；Finally product is detached, removes lower floor's water phase and resin, takes oil phase, washing oil
Mutually to get oil-soluble molybdenum base catalyst precursor.The vulcanization active component of cobalt of presoma autovulcanization production, grain size is smaller, energy
Be highly dispersed in heavy oil, there is higher hydrogenation activity, can preferably inhibit the generation of coke, addition can reach on a small quantity compared with
Good suppression coke effect.But the phosphorus pentasulfide that this method is selected has severe toxicity, and hydrogen sulfide gas can be generated in reaction process, it is right
Human body and environment damage, and preparation process is cumbersome, and product separating difficulty is big, of high cost, are not suitable for industrial production.
Invention content
Therefore, the technical problem to be solved in the present invention is raw material severe toxicity of the prior art is overcome to be easy to human body and ring
Border damages, product separation is difficult, preparation process is cumbersome, is unsuitable for the defects of industrial production, so as to provide a kind of phosphate
Class poor oil floating bed hydrogenation oil-soluble catalyst and its preparation method and application.
In order to solve the above technical problems, the present invention uses following specific technical solution：
A kind of phosphoric acid ester floating bed hydrogenation oil-soluble catalyst, using phosphoric acid ester as organic ligand, with molybdenum source chemical combination
Object provides active component, wherein, the molar ratio in phosphoric acid ester organic ligand in P elements and molybdenum source compound between molybdenum element
It is 1:1~1:5.
Further, the phosphoric acid ester organic ligand is di (isooctyl) phosphate or diphenyl phosphate.
Further, the molybdenum source compound is phosphomolybdic acid or sodium molybdate.
A kind of preparation method of above-mentioned phosphoric acid ester floating bed hydrogenation oil-soluble catalyst, which is characterized in that using ethyl alcohol
As reaction dissolvent, it is prepared by circumfluence method.
Further, following steps are specifically included：
(1) organophosphor esters ligand is dissolved in absolute ethyl alcohol, obtains phosphoric acid ester organic ligand solution；
(2) according to P/Mo molar ratios 1:1-1:5 weigh molybdenum source compound, and be dissolved in absolute ethyl alcohol, ultrasonic disperse 10-
30min obtains molybdenum source solution；
(3) the phosphoric acid ester organic ligand solution of step (1) is slowly added into molybdenum source solution while stirring, be added dropwise
Reaction system pH=1-6 is maintained in the process, 80-120 DEG C is warming up to after being added dropwise, and is continued to stir 4-8h, then be stood
8-24h；
(4) isolated liquid catalyst be dried in vacuo up to the oil-soluble catalyst.
Further, the mass ratio of phosphoric acid ester organic ligand and absolute ethyl alcohol is 1 in step (1):3-1:5.
Further, the mass ratio of molybdenum source compound and absolute ethyl alcohol is 1 in step (2):1.5-1:8.
Further, the rate of addition of phosphoric acid ester organic ligand solution is 0.5-2ml/min in step (3), and stirring is fast
It spends for 200-400r/min..
Further, the vacuum drying temperature is 80-120 DEG C, drying time 6-24h.
A kind of application of above-mentioned phosphoric acid ester floating bed hydrogenation oil-soluble catalyst in poor oil catalytic hydrogenation reaction,
It is characterized in that, reaction initial hydrogen pressure is 8-15MPa, and stir speed (S.S.) 400-800r/min, curing temperature is 300-400 DEG C, vulcanization
Time is 10-40min, 350-500 DEG C of reaction temperature, reaction time 60-120min.
Technical solution of the present invention has the following advantages that：
1. phosphoric acid ester floating bed hydrogenation oil-soluble catalyst provided by the invention has good oil-soluble, can be dissolved in
In poor oil, and can be dispersed in poor oil, when reaction, comes into full contact with poor oil and hydrogen, activated centre from
It is directly generated in the thermal decomposition of catalyst, can reach very high degree of dispersion, so as to improve catalyst activity, more effectively inhibit coking.
2. the preparation method of phosphoric acid ester floating bed hydrogenation oil-soluble catalyst provided by the invention, with phosphoric acid ester chemical combination
Object, mainly using more acid compounds as molybdenum source, oil-soluble weight is obtained by being refluxed, after vacuum drying as organic ligand
Matter oil hydrogenation catalysts.Materials safety does not generate pernicious gas in reaction process, and making step is simple, and product separation is easy, behaviour
Facilitate, it is at low cost, conducive to industrialized production and application are realized.
3. phosphoric acid ester floating bed hydrogenation oil-soluble catalyst provided by the invention is applied to the floating bed hydrogenation of poor oil
In the process, it is high to removal rates such as metal, sulphur, nitrogen and coking can be inhibited.
Specific embodiment
It is to preferably further understand the present invention to provide following embodiments, it is not limited to the best embodiment party
Formula is not construed as limiting present disclosure and protection domain, anyone the present invention enlightenment under or by the present invention and its
The feature of his prior art be combined and obtain it is any with the present invention it is same or similar as product, all fall within the present invention
Within protection domain.
Specific experiment step or condition person are not specified in embodiment, according to the described routine experiment of document in the art
The operation of step or condition can carry out.Reagents or instruments used without specified manufacturer, being can be by acquisition purchased in market
Conventional reagent product.
Embodiment 1
The present embodiment provides one kind with di (isooctyl) phosphate (P204) as phosphoric acid ester organic ligand, with phosphomolybdic acid (Pma)
As the poor oil floating bed hydrogenation oil-soluble catalyst of molybdenum source compound, the active component after vulcanization is Mo-S phases.
Preparation method includes the following steps：
(1) di (isooctyl) phosphate (P of 3.312g is weighed204) be dissolved in 15ml absolute ethyl alcohols, 30min is stirred after dissolving and is obtained
To mixed solution.
(2) then according to P/Mo molar ratios 1:1, which weighs 1.577g phosphomolybdic acids (Pma), is dissolved in 15ml absolute ethyl alcohols, dissolving
It is poured into three neck round bottom flask after ultrasonic disperse 20min.
(3) three mouthfuls of circles being slowly added into above-mentioned mixed solution with the speed of 1ml/min by peristaltic pump in step (2)
In the flask of bottom, and it is vigorously stirred.Above-mentioned reaction system pH=2 or so is maintained during being added dropwise, is heated up after being added dropwise
To 110 DEG C, continue to stand 12h after stirring 7h.
(4) after standing and finishing, obtained product is placed in vacuum drying chamber, is risen to the rate of 2.5 DEG C/min
120 DEG C of vacuum drying 12h, obtain Pma-P204(1:1), it is denoted as catalyst A.
Embodiment 2
The present embodiment provides one kind with di (isooctyl) phosphate (P204) as phosphoric acid ester organic ligand, with phosphomolybdic acid (Pma)
As the poor oil floating bed hydrogenation oil-soluble catalyst of molybdenum source compound, the active component after vulcanization is Mo-S phases.
Preparation method includes the following steps：
(1) di (isooctyl) phosphate (P of 3.312g is weighed204) be dissolved in 15ml absolute ethyl alcohols, 30min is stirred after dissolving and is obtained
To mixed solution.
(2) then according to P/Mo molar ratios 1:2, which weigh 3.155g phosphomolybdic acids (Pma), is dissolved in 15ml absolute ethyl alcohols, dissolving
It is poured into three neck round bottom flask after ultrasonic disperse 20min.
(3) three mouthfuls of circles being slowly added into above-mentioned mixed solution with the speed of 1ml/min by peristaltic pump in step (2)
In the flask of bottom, and it is vigorously stirred.Above-mentioned reaction system pH=3 or so is maintained during being added dropwise, is heated up after being added dropwise
To 120 DEG C, continue to stand 11h after stirring 8h.
(4) after standing and finishing, obtained product is placed in vacuum drying chamber, is risen to the rate of 2.5 DEG C/min
120 DEG C of vacuum drying 12h, obtain Pma-P204(1:2), it is denoted as catalyst B.
Embodiment 3
The present embodiment provides one kind with di (isooctyl) phosphate (P204) as phosphoric acid ester organic ligand, with phosphomolybdic acid (Pma)
As the poor oil floating bed hydrogenation oil-soluble catalyst of molybdenum source compound, the active component after vulcanization is Mo-S phases.
Preparation method includes the following steps：
(1) di (isooctyl) phosphate (P of 3.312g is weighed204) be dissolved in 15ml absolute ethyl alcohols, 30min is stirred after dissolving and is obtained
To mixed solution.
(2) then according to P/Mo molar ratios 1:3, which weigh 4.733g phosphomolybdic acids (Pma), is dissolved in 15ml absolute ethyl alcohols, dissolving
It is poured into three neck round bottom flask after ultrasonic disperse 20min.
(3) three mouthfuls of circles being slowly added into above-mentioned mixed solution with the speed of 1ml/min by peristaltic pump in step (2)
In the flask of bottom, and it is vigorously stirred.Reaction system pH=2 or so is maintained during being added dropwise, 120 are warming up to after being added dropwise
DEG C, continue to stand 12h after stirring 8h.
(4) after standing and finishing, obtained product is placed in vacuum drying chamber, is risen to the rate of 2.5 DEG C/min
120 DEG C of vacuum drying 14h, obtain Pma-P204(1:3), it is denoted as catalyst C.
Embodiment 4
The present embodiment provides one kind with di (isooctyl) phosphate (P204) as phosphoric acid ester organic ligand, with phosphomolybdic acid (Pma)
As the poor oil floating bed hydrogenation oil-soluble catalyst of molybdenum source compound, the active component after vulcanization is Mo-S phases.
Preparation method includes the following steps：
(1) di (isooctyl) phosphate (P of 3.312g is weighed204) be dissolved in 15ml absolute ethyl alcohols, 30min is stirred after dissolving and is obtained
To mixed solution.
(2) then according to P/Mo molar ratios 1:4, which weigh 6.310g phosphomolybdic acids (Pma), is dissolved in 15ml absolute ethyl alcohols, dissolving
It is poured into three neck round bottom flask after ultrasonic disperse 20min.
(3) three mouthfuls of circles being slowly added into above-mentioned mixed solution with the speed of 1ml/min by peristaltic pump in step (2)
In the flask of bottom, and it is vigorously stirred.Above-mentioned reaction system pH=2 or so is maintained during being added dropwise, is heated up after being added dropwise
To 120 DEG C, continue to stand 11h after stirring 9h.
(4) after standing and finishing, obtained product is placed in vacuum drying chamber, is risen to the rate of 2.5 DEG C/min
120 DEG C of vacuum drying 12h, obtain Pma-P204(1:4), it is denoted as catalyst D.
Embodiment 5
The present embodiment provides one kind using diphenyl phosphate (DpH) as phosphoric acid ester organic ligand, made with phosphomolybdic acid (Pma)
For the poor oil floating bed hydrogenation oil-soluble catalyst of molybdenum source compound, the active component after vulcanization is Mo-S phases.
Preparation method includes the following steps：
(1) diphenyl phosphate (DpH) for weighing 2.569g is dissolved in 15ml absolute ethyl alcohols, and 30min is stirred after dissolving and is obtained
Mixed solution.
(2) then according to P/Mo molar ratios 1:1, which weighs 1.577g phosphomolybdic acids (Pma), is dissolved in 15ml absolute ethyl alcohols, dissolving
It is poured into three neck round bottom flask after ultrasonic disperse 20min.
(3) three mouthfuls of circles being slowly added into above-mentioned mixed solution with the speed of 1ml/min by peristaltic pump in step (2)
In the flask of bottom, and it is vigorously stirred.Above-mentioned reaction system pH=2 or so is maintained during being added dropwise, is heated up after being added dropwise
To 120 DEG C, continue to stand 12h after stirring 8h.
(4) after standing and finishing, obtained product is placed in vacuum drying chamber, is risen to the rate of 2.5 DEG C/min
120 DEG C of vacuum drying 12h, obtain DpH-Pma (1:1), it is denoted as catalyst E.
Embodiment 6
The present embodiment provides one kind with di (isooctyl) phosphate (P204) as phosphoric acid ester organic ligand, with sodium molybdate (Ma-
Na) as the poor oil floating bed hydrogenation oil-soluble catalyst of molybdenum source compound, the active component after vulcanization is Mo-S phases.
Preparation method includes the following steps：
(1) di (isooctyl) phosphate (P of 3.312g is weighed204) be dissolved in 15ml absolute ethyl alcohols, 30min is stirred after dissolving and is obtained
To mixed solution.
(2) then according to P/Mo molar ratios 1:1, which weighs 2.485g sodium molybdates (Ma-Na), is dissolved in 15ml absolute ethyl alcohols, molten
It is poured into three neck round bottom flask after solution ultrasonic disperse 20min.
(3) three mouthfuls be slowly added into above-mentioned mixed solution with the speed of 1.5ml/min by peristaltic pump in step (2)
In round-bottomed flask, and it is vigorously stirred.Reaction system pH=2 or so is maintained during being added dropwise, is warming up to after being added dropwise
130 DEG C, continue to stand 12h after stirring 10h.
(4) after standing and finishing, obtained product is placed in vacuum drying chamber, is risen to the rate of 2.5 DEG C/min
120 DEG C of vacuum drying 12h, obtain P204(Ma-Na) is denoted as catalyst F.
Embodiment 7
The present embodiment provides one kind using diphenyl phosphate (DpH) as organophosphor ligand, using sodium molybdate (Ma-Na) as molybdenum
The poor oil floating bed hydrogenation oil-soluble catalyst of source compound, the active component after vulcanization are Mo-S phases.
Preparation method includes the following steps：
(1) diphenyl phosphate (DpH) for weighing 2.569g is dissolved in 15ml absolute ethyl alcohols, and 30min is stirred after dissolving and is obtained
Mixed solution.
(2) then according to P/Mo molar ratios 1:1, which weighs 2.485g sodium molybdates (Ma-Na), is dissolved in 15ml absolute ethyl alcohols, molten
It is poured into three neck round bottom flask after solution ultrasonic disperse 20min.
(3) three mouthfuls of circles being slowly added into above-mentioned mixed solution with the speed of 2ml/min by peristaltic pump in step (2)
In the flask of bottom, and it is vigorously stirred.Reaction system pH=2 or so is maintained during being added dropwise, 120 are warming up to after being added dropwise
DEG C, continue to stand 12h after stirring 8h.
(4) after standing and finishing, obtained product is placed in vacuum drying chamber, is risen to the rate of 2.5 DEG C/min
120 DEG C of vacuum drying 12h, obtain DpH- (Ma-Na), are denoted as catalyst G.
Comparative example 1
Present embodiments provide a kind of hydrogenation catalyst and preparation method thereof.The hydrogenation catalyst is by organic phosphoric acid and molybdenum source
Bonding obtains after reacted, wherein, organic phosphoric acid is dihexylamine methyl acid phosphate, and molybdenum source is ammonium heptamolybdate, the phosphorus in organic phosphoric acid
The molar ratio of element and molybdenum element in molybdenum source is 1:1；
The preparation method of above-mentioned hydrogenation catalyst, includes the following steps：
1) the dihexylamine methyl acid phosphate of 0.005mol is weighed, and is placed it in single-necked flask, adding in 30mL ethyl alcohol makes it
It is completely dissolved；
The ammonium heptamolybdate of 0.44g is weighed, and is added into above-mentioned single-necked flask；
2) spherical condensation tube, whipping step 1 are placed above above-mentioned single-necked flask) in obtained mixture, and will mixing
Object, which is warming up to 80 DEG C, makes its reflux, stops reaction after keeping 4h；
3) it treats that the temperature of the reaction product obtained in step 2) is down to room temperature, adds in distilled water, centrifugal filtration continues with steaming
Distilled water is washed for several times；
4) reaction product after washing in step 3) at 90 DEG C is dried in vacuo 5h, hydrogenation catalyst is made, is denoted as and urges
Agent H.
Comparative example 2
This comparative example provides a kind of hydrogenation catalyst and preparation method thereof.The hydrogenation catalyst is passed through by organic acid and molybdenum source
Bonding obtains after reaction, wherein, organic acid is dihexylamine acetic acid, and molybdenum source is ammonium heptamolybdate, P elements and molybdenum in organic phosphoric acid
The molar ratio of molybdenum element is 1 in source:2；
The preparation method of above-mentioned hydrogenation catalyst, includes the following steps：
1) the dihexylamine acetic acid of 0.005mol is weighed, and is placed it in single-necked flask, adding in 30mL ethyl alcohol makes it completely
Dissolving；
The ammonium heptamolybdate of 0.44g is weighed, and is added into above-mentioned single-necked flask；
2) spherical condensation tube, whipping step 1 are placed above above-mentioned single-necked flask) in obtained mixture, and will mixing
Object, which is warming up to 80 DEG C, makes its reflux, stops reaction after keeping 4h；
3) it treats that the temperature of the reaction product obtained in step 2) is down to room temperature, adds in distilled water, centrifugal filtration continues with steaming
Distilled water is washed for several times；
4) reaction product after washing in step 3) at 90 DEG C is dried in vacuo 5h, hydrogenation catalyst is made, is denoted as and urges
Agent I.
Experimental example
1. oil-soluble is tested
Embodiment is prepared into gained catalyst (A-G) and is dissolved in ethyl alcohol etc. respectively with comparative example preparation gained catalyst (H-I)
In organic solvent.It is found by comparison, present invention preparation gained catalyst, which can be stablized, to be dissolved in organic solvent and formed
Phase system has good oil-soluble.And gained catalyst is prepared by comparative example and is only capable of being dissolved in the larger organic solvent of dissolubility
In, oil-soluble is poor.
2. catalytic activity is tested
The catalyst number consecutively that embodiment 1-7 and comparative example 1-2 are prepared is A-I, using by Yantai Pine Ridge
Autoclave (KCFD02-03, volume 0.2L, heating power 3kW, the design pressure of Chemical Equipment Co., Ltd.'s production
35MPa, 600 DEG C of design temperature and the vacuum distillation analyzer (SYD- produced by Shanghai Changji Geological Instrument Co., Ltd.
Activity rating is carried out to above-mentioned catalyst on 0165A).
Activity rating specific experiment is as follows：
First by 44g reduced crudes, the oil-soluble catalyst that amount containing molybdenum is 0.00065mol and 0.2g sublimed sulfurs in height
It is stirred evenly in fast refiner for active testing, is first passed through hydrogen pressure is made in kettle to reach 24MPa and hunt leak, discharge simultaneously
Air in kettle, being re-filled with hydrogen makes to reach certain pressure in kettle, is warming up to reaction temperature, reacts certain under certain stir speed (S.S.)
Stop heating and stirring after time, use water-cooling pattern that temperature in the kettle is rapidly decreased to room temperature to terminate reaction.Wherein, activity is surveyed
Strip part：Initial hydrogen pressure 12MPa, stir speed (S.S.) 600r/min, curing temperature are respectively 350 DEG C, vulcanization time 90min, instead
Answer 440 DEG C of temperature, reaction time 120min.The product collected after the completion of reaction in reaction kettle carries out vacuum distillation test, distills
After in toluene supersound washing distilling flask residual oil (>500 DEG C), it is burnt to obtain liquid phase after centrifugation, drying.
The catalytic activity of catalyst is evaluated with following index：
Total recovery=(obtained distillate+gas recovery ratio)/raw material oil quality × 100%
Liquid oil quality/raw material oil quality × 100% below fraction oil yield=500 DEG C of boiling point
Metal removal rate=(tenor in tenor/feedstock oil in 1- liquid oils) × 100%
Desulfurization degree=(sulfur content in sulfur content/feedstock oil in 1- liquid oils) × 100%
Denitrification percent=(nitrogen content in nitrogen content/feedstock oil in 1- liquid oils) × 100%
Coking rate (toluene insolubles)=solid residue/raw material oil quality × 100%.
The evaluation index of 1 poor oil suspension bed hydrogenation catalyst of table
Table 1 is added for the mink cell focus suspension bed of catalyst prepared in embodiment 1-7 and comparative example 1,2 using the method for the present invention
The evaluation index of hydrogen catalyst.
As it can be seen from table 1 mink cell focus suspension bed hydrogenation catalyst (sample A-G) mink cell focus of the present invention can reach
To higher total recovery, the total recovery of wherein sample C may be up to 98.74%, and fraction oil yield of the boiling point below 500 DEG C is reachable
80.07%, at the same time, to metal, sulphur, nitrogen component removal efficiency respectively be up to 96.3%, 94.55%, 93.77%, and
With relatively low coking rate, so as to show higher hydrogenation activity.It is compared with comparative sample 2, obtained mink cell focus total recovery
Only 65.47%, hydrogenation activity is poor.
Obviously, the above embodiments are merely examples for clarifying the description, and is not intended to 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 the obvious variation thus extended out or
Among changing still in the protection domain of the invention.
Claims (11)
1. a kind of phosphoric acid ester floating bed hydrogenation oil-soluble catalyst, which is characterized in that using phosphoric acid ester as organic ligand, with
Molybdenum source compound provides active component, wherein, in phosphoric acid ester organic ligand in P elements and molybdenum source compound between molybdenum element
Molar ratio be 1:1~1:5.
2. phosphoric acid ester floating bed hydrogenation oil-soluble catalyst according to claim 1, which is characterized in that the phosphate
Class organic ligand is di (isooctyl) phosphate or diphenyl phosphate.
3. phosphoric acid ester floating bed hydrogenation oil-soluble catalyst according to claim 1, which is characterized in that the molybdenum source
It is phosphomolybdic acid or sodium molybdate to close object.
4. a kind of preparation method of claim 1-3 any one of them phosphoric acid ester floating bed hydrogenation oil-soluble catalyst,
It is characterized in that, using ethyl alcohol as reaction dissolvent, is prepared by circumfluence method.
5. the preparation method of phosphoric acid ester floating bed hydrogenation oil-soluble catalyst according to claim 4, which is characterized in that packet
Include following steps：
(1) organophosphor esters ligand is dissolved in absolute ethyl alcohol, obtains phosphoric acid ester organic ligand solution；
(2) according to P/Mo molar ratios 1:1-1:5 weigh molybdenum source compound, and be dissolved in absolute ethyl alcohol, ultrasonic disperse 10-30min,
Obtain molybdenum source solution；
(3) the phosphoric acid ester organic ligand solution of step (1) is slowly dropped in molybdenum source solution while stirring, in the process of dropwise addition
Middle maintenance reaction system pH=1-6, is warming up to 80-120 DEG C after being added dropwise, and continues to stir 4-8h, then stands 8-
24h；
(4) isolated liquid catalyst be dried in vacuo up to the oil-soluble catalyst.
6. the preparation method of phosphoric acid ester floating bed hydrogenation oil-soluble catalyst according to claim 5, which is characterized in that
The mass ratio of phosphoric acid ester organic ligand and absolute ethyl alcohol is 1 in step (1):3-1:5.
7. the preparation method of phosphoric acid ester floating bed hydrogenation oil-soluble catalyst according to claim 5, which is characterized in that
The mass ratio of molybdenum source compound and absolute ethyl alcohol is 1 in step (2):1.5-1:8.
8. the preparation method of phosphoric acid ester floating bed hydrogenation oil-soluble catalyst according to claim 5, which is characterized in that
The addition speed of phosphoric acid ester organic ligand solution is 0.5-2ml/min, mixing speed 200-400r/min in step (3).
9. the preparation method of phosphoric acid ester floating bed hydrogenation oil-soluble catalyst according to claim 5, which is characterized in that
The vacuum drying temperature is 80-120 DEG C, drying time 6-24h.
10. any one of any one of the claim 1-3 phosphoric acid ester floating bed hydrogenation oil-soluble catalysts or claim 4-9
The phosphoric acid ester floating bed hydrogenation oil-soluble catalyst that the preparation method is prepared is in poor oil catalytic hydrogenation reaction
Using.
11. phosphoric acid ester floating bed hydrogenation oil-soluble catalyst according to claim 10 is in poor oil catalytic hydrogenation reaction
In application, which is characterized in that reaction initial hydrogen pressure be 8-15MPa, stir speed (S.S.) 400-800r/min, curing temperature 300-
400 DEG C, vulcanization time 10-40min, 350-500 DEG C of reaction temperature, reaction time 60-120min.
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