CN107868108A - A kind of organic-molybdenum salt and preparation method thereof - Google Patents
A kind of organic-molybdenum salt and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic System
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic System compounds without a metal-carbon linkage
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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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J37/20—Sulfiding
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- C07—ORGANIC CHEMISTRY
- 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
- C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C219/06—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having the hydroxy groups esterified by carboxylic acids having the esterifying carboxyl groups bound to hydrogen atoms or to acyclic carbon atoms of an acyclic saturated carbon skeleton
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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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/09—Complexes with metals
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
Abstract
A kind of organic-molybdenum salt and preparation method thereof; the organic-molybdenum salt is a kind of molybdenum amine complex; containing+6 valency molybdenum ions, the acyl group combined with molybdenum ion and with the amido that alkyl is combined in described acyl group, wherein the mass fraction of molybdenum be the organic-molybdenum salt 10%~30%.Catalyst precarsor of the organic-molybdenum salt provided by the invention as Residue Hydrotreating Technology, hydrogenation conversion is high, meanwhile, the compound has excellent antiwear and friction reduction property and good corrosion inhibition for metal, can be used as water-soluble lube oil additive.The preparation method of water-soluble organic-molybdenum salt is simple, and synthesis path is nontoxic, environmentally friendly, and product separation is simple.
Description
Technical field
The present invention relates to a kind of organic matter containing molybdenum and preparation method thereof, combined more specifically to a kind of organic-molybdenum salt
Thing and preparation method thereof.
Background technology
It is continuously increased with the depth of oil exploitation, the crude oil that oilfield exploitation goes out increasingly heaviness, in poor quality, this quasi-oil
In the sulphur, nitrogen, the tenor that contain it is high, carbon residue is high, is difficult to using devices such as the fixed bed hydrogenation of routine, catalytic cracking
This quasi-oil.At the same time, people are increasing to the demand of light-end products, in this case, heavy crude carried out deep
Processing, the problem of improving the utilization rate of resource turns into people's growing interest.Heavy Oil Processing Technology is divided into two classes：Decarburization and hydrogenation,
In order to further improve light oil yield, hydrogenation technique plays more and more important effect in mink cell focus manufacture field.Hydrogenation technique
Including fixed bed, moving bed, ebullated bed, slurries bed process, wherein, the development of fixed bed hydrogenation technology is most ripe, but it is to raw material
Bad adaptability, processing high metal, high carbon residue raw material when, can accelerator activator inactivation, cause a large amount of green cokes.And slurry bubble bed
It is good to the adaptability of raw material, high-sulfur, high metal, the inferior raw material of high carbon residue can be handled, there is preferable development prospect.In early days
The residual oil slurry bubble bed hydrogenation technique of exploitation mainly uses solid particle or additive as catalyst, such as coal dust, ferrous sulfate, ore
Powder, etc., this kind of catalyst is the relatively low mineral of hydrogenation activity, and catalyst charge is larger, causes tailings amount big, and solid content is high,
It is difficult to handle.Slurries bed process often uses disperse type catalyzer, and the particle diameter that disperse type catalyzer is dispersed in heavy oil is very small (sub-
Micron order) metal sulfide grain, due to catalyst, decentralization is high in heavy oil, and catalyst granules activation hydrogen and saturation are divided greatly
The ability of sub- free radical greatly enhances, and these catalyst precursors mix with residual oil, and suspended in the pressure of certain hydrogen by thermosetting
Sulfide type catalyst, the presoma of these catalyst is mainly the water-soluble and class of oil-soluble two.With slurry bubble bed residual hydrogenation
The development of technique, the hydrogenation activity and cost of the catalyst used in technical process turn into influence technological operation cost it is important because
Element.Water-soluble molybdenum based compound cost is less than oil-soluble molybdenum series catalysts, in hydrogenation process under relatively low dosage have compared with
Good hydrogenation activity.
Water-soluble catalyst mainly has water-soluble machine metallic compound, and this kind of compound falls within water-soluble lubricating oil and added
Add agent, in recent years, in view of the development and application of water-soluble lubricating oil additive, the research of water-soluble lubricating oil additive achieve
Certain progress, this lubricant are mainly used in the process of metal working such as cutting, drawing, grinding, rolling and hydraulic drive field.
Water-soluble organic molybdenum has preferable hydrogenation activity, therefore is gradually used for residual hydrogenation and coal field of hydrogenation.
As catalyst precursor, during water-soluble organic-molybdenum salt use, the metallic compound aqueous solution is typically passed through into shearing first
Then emulsion dispersion is dehydrated, vulcanized, form the feed residue containing the metallic catalyst after vulcanization, metal Mo into residual oil
Hydrogenation activity be higher than other transition metal, such as Ni, V, Co.
Patent CN1360013A discloses a kind of water-soluble organic-molybdenum extreme pressure, wear-resistant, wear reducing additive, mainly contains oil
Acid, diethanol amine molybdic acid, oleic acid diethanol amine thiophosphate, by using oleic acid, diethanol amine, thiophosphate, molybdic acid
Reaction, brown viscous liquid product is prepared, the product can be used for water based lubrication system, can it be used for residual hydrogenation and
Its performance is not set out, simultaneously as being unfavorable for giving birth on a large scale during residual hydrogenation containing sulphur, P elements in the system
Production and use.Patent CN104667954A discloses a kind of method of the water-soluble ammonium molybdate prepared using rich molybdenum ore, mainly
It is that selected rich molybdenum ore is added to excessive NH4Obtained in OH solution, after reaction by processing a kind of absinthe-green water-soluble
Property ammonium molybdate, the water-soluble ammonium molybdate can be used for residual hydrogenation, but the water-soluble ammonium molybdate catalyst particle diameter be 3.0~
4.5mm, particle diameter is larger, is unfavorable for dissolving during the course of the reaction and disperses, is not suitable for slurry bubble bed hydrogenation technique.
CN1053460A disclose it is a kind of be used for weight, the dispersed catalyst of residual oil catalytic hydrogenation, mainly by the metals such as Mo, Ni aoxidize
Thing or inorganic salts are dissolved in water in acid condition, are prepared into the aqueous solution containing metal 2~15%, then emulsify the aqueous solution
It is distributed in weight, residual oil, enters back into floating bed hydrogenation reactor.Mixed feeding is entered under the conditions of 5~20MPa, 380~460 DEG C
Row hydrogenation reaction, not in the case of green coke, more than 70% yield of light oil can be being obtained, but the catalyst forms substantially
In contain P elements, in slurry bubble bed residual hydrogenation equipment, dosage is larger, is difficult to meet in the production and use process increasingly harsh
Energy-conserving and environment-protective requirement.
Existing water-soluble organic-molybdenum salt is mainly used in lubricating area, but the water-soluble organic-molybdenum salt developed is big
It is exist due to etching problem and environmental issue caused by the presence of the compounds such as sulphur phosphorus more.Water-soluble catalyst has preferably catalysis
Hydrogenation, price are relatively inexpensive, the advantages that easily preparing, and can reduce the running cost of slurry bubble bed Residue Hydrotreating Technology, still
Scattered situation of the Water-soluble Dispersed in residual oil can directly influence catalyst sulfided state and catalyst in course of reaction
In activity.Therefore, exploitation have it is more preferably water-soluble, being capable of dispersed no sulphur phosphorus water-solubility organic-molybdenum salt pair in residual oil
Slurry bubble bed Residue Hydrotreating Technology has great importance.
The content of the invention
One of technical problems to be solved of the present invention are to provide a kind of organic-molybdenum salt, face hydrogen in heavy oil after presulfurization
Excellent Hydrogenation is shown in thermal conversion processes.The second technical problem to be solved by the present invention be to provide one kind prepare it is above-mentioned
The preparation method of organic-molybdenum salt.
A kind of organic-molybdenum salt compound provided by the invention, the organic-molybdenum salt are a kind of molybdenum amine complexes, contain+6 valency molybdenums
Ion, the acyl group combined with molybdenum ion and with the amido that alkyl is combined in described acyl group, wherein the mass fraction of molybdenum for should
The 10%~30% of organic-molybdenum salt.
The preparation method of above-mentioned organic-molybdenum salt, comprises the following steps：
(1) 30~70 DEG C are cooled to after reacting C6~C18 ester and alcohol amine compound at 90 DEG C~150 DEG C；
(2) by the dissolving of sexavalence molybdenum source compound in a solvent, the mass ratio of solvent and sexavalence molybdenum source compound for (0.5~
5):1, alkaline solution is then added, alkali and the mass ratio of sexavalence molybdenum source compound are (0.01~0.1)：1, described solvent is
Benzene, toluene, water, ethanol or petroleum ether；
(3) solution of step (2) is added in step (1) reacted solution, under the conditions of temperature is 50~100 DEG C
Reaction, reacts under the conditions of being then warming up to 100~150 DEG C again；
(4) reaction product is subjected to extract and separate, it is organic-molybdenum salt that lower floor's liquid is obtained after separation.
Organic-molybdenum salt provided by the invention has the beneficial effect that：
Organic-molybdenum salt provided by the invention is water-soluble organic-molybdenum salt, can be as the catalysis of slurry bubble bed Residue Hydrotreating Technology
Agent precursor, emulsion is formed after disperseing with residual oil, emulsifier, and sedimentation is not produced with catalyst precarsor under reaction condition heating
And precipitation, after stripping the removing moisture that is demulsified, the catalyst that presulfurization is formed can be dispersed in feedstock oil, avoids
The aggregation of catalyst, so as to improve hydrogenation conversion.Meanwhile the compound has excellent antiwear and friction reduction property and good
Corrosion inhibition for metal, it can be used as water-soluble lube oil additive.
The preparation method of organic-molybdenum salt provided by the invention has the beneficial effect that：
The preparation method of organic-molybdenum salt provided by the invention is simple, and the compound synthesis path is nontoxic, environmentally friendly, the compound
With fabulous aqueous stability, course of reaction high conversion rate, product separation is simple in building-up process.
Brief description of the drawings
Fig. 1 is the infrared spectrogram for the organic-molybdenum salt sample being prepared in embodiment 1.
Fig. 2 is the infrared spectrogram for the organic-molybdenum salt sample being prepared in embodiment 2.
Embodiment
The present invention provides one kind has good water-soluble and higher gold without sulphur without Phosphorus organic-molybdenum salt, the organic-molybdenum salt
Belong to content, while the organic-molybdenum salt faces in hydrogen thermal cracking process in heavy oil and can be dispersed in residual oil, in hydrogenation process
Show excellent suppression Jiao's performance.
The present invention provides a kind of organic-molybdenum salt, and the organic-molybdenum salt is a kind of molybdenum amine complex, contains+6 valency molybdenum ions and molybdenum
The acyl group of ions binding and with the amido that alkyl is combined in described acyl group, the wherein mass fraction of molybdenum is the organic-molybdenum salt
10%~30%.
The preparation method of above-mentioned organic-molybdenum salt, comprises the following steps：
(1) 30~70 DEG C are cooled to after reacting C6~C18 ester and alcohol amine compound at 90 DEG C~150 DEG C；
(2) by the dissolving of sexavalence molybdenum source compound in a solvent, the mass ratio of solvent and sexavalence molybdenum source compound for (0.5~
5):1, alkaline solution is then added, alkali and the mass ratio of sexavalence molybdenum source compound are (0.01~0.1)：1, described solvent is
Benzene, toluene, water, water, ethanol or petroleum ether；
(3) solution of step (2) is added in step (1) reacted solution, under the conditions of temperature is 50~100 DEG C
Reaction, reacts under the conditions of being then warming up to 100~150 DEG C again；
(4) reaction product is subjected to extract and separate, it is organic-molybdenum salt that lower floor's liquid is obtained after separation.
The preparation method of organic-molybdenum salt provided by the invention, it is preferable that step (1) C6~C18 ester and sexavalence molybdenum source
The mol ratio of compound is (2~8)：1；Alcohol amine compound and the mol ratio of sexavalence molybdenum source compound are (2~8)：1.Preferably, will
C6~C18 ester be cooled to after being reacted 1~6 hour at 90 DEG C~150 DEG C with alcohol amine compound 30~70 DEG C it is standby.
Step (2) dissolves sexavalence molybdenum source in a solvent, and solvent and the mass ratio of sexavalence molybdenum source compound are (0.5~5):
1, then in middle addition alkaline solution, alkali and the mass ratio of sexavalence molybdenum source are (0.01~0.1)：1, described solvent is benzene, first
Benzene, water, ethanol or petroleum ether.
Then the solution of step (2) is added in step (1) reacted solution by step (3), it is preferable that the addition time
For 2~40min, it is stirred continuously in adding procedure, after addition, is reacted 2~7 hours under the conditions of being 50~100 DEG C in temperature
Afterwards；Reacted 1~6 hour under the conditions of being warming up to 100~150 DEG C again.
Reaction product is carried out extract and separate by final step (4), and lower floor's blueness thick liquid is obtained after separation as synthesis
Water-soluble organic-molybdenum salt.
In the preparation method of organic-molybdenum salt provided by the invention, the ester of the C6~C18 is selected from butyl acetate, sad first
Ester, amyl acetate, amyl valerate, ethyl butyrate, isoamyl acetate, cognac oil, methyl valerate, amyl caproate, ethyl caprilate
With one or more of mixtures in ethyl valerate.The sexavalence molybdenum source compound be selected from molybdic acid, ammonium molybdate, ammonium paramolybdate and
One or more in molybdenum trioxide.
In the preparation method of organic-molybdenum salt provided by the invention, the alkaline solution is selected from sodium carbonate, sodium acid carbonate, hydrogen-oxygen
Change potassium or sodium hydrate aqueous solution.
Organic-molybdenum salt provided by the invention can be as the catalyst precursor of residual hydrocracking, can be equal after presulfurization
It is even to be dispersed in residual oil, there is preferable Hydrogenation.The preparation method of organic-molybdenum salt provided by the invention is simple, water-soluble
Good, course of reaction high conversion rate, product is without filtration step.
The following examples will be further described to method provided by the invention, but therefore not limit this hair
It is bright.
Each raw material used in embodiment and comparative example is Chemical Reagent Co., Ltd., Sinopharm Group's product.Implement
The residual oil raw material property used in example and comparative example is shown in Table 1.
Embodiment 1
1) cognac oil will be preheated to 65 DEG C, diethyl ethylene diamine, cognac oil and three oxygen are added into cognac oil
Change molybdenum mol ratio and be equal to 4：1, diethyl ethylene diamine is equal to 4 with molybdenum trioxide according to mol ratio：1, reacted 3 hours at 140 DEG C
After be cooled to 60 DEG C it is standby；2) add solvent in molybdenum trioxide to disperse, the mass ratio of solvent and molybdenum trioxide is 4：1, then
The mass ratio of dropwise addition sodium hydroxide solution, sodium hydroxide and molybdenum trioxide is 0.05：1；3) solution 2) is added to and 1) obtained
Product in, add 20 minutes time, in adding procedure, be stirred continuously, after addition, temperature be 90 DEG C under the conditions of react
3 hours；Then reacted 2 hours under the conditions of being warming up to 115 DEG C again；After reaction terminates, obtained reaction product is subjected to extraction point
From it is synthesized organic-molybdenum salt that lower floor's blueness thick liquid is obtained after separation.
Metal content analysis (analysis method GB/T 17476 is carried out to product using inductive coupling plasma emission spectrum method
Equivalence margin ASTMD 5185-95), analysis result, molybdenum content is 18.8wt% in product.Dissolubility is shown in Table 2.Products therefrom
Infrared spectrum is shown in Fig. 1, it can be seen from figure 1 that in 3300-3500cm-1Nearby there are N-H stretching vibration peak, 1650cm-1Nearby there is N-H
Deformation vibration bands of a spectrum, in 930cm-1、840cm-1Nearby there is Mo (O) absworption peak.
Embodiment 2
1) methyl caprylate is preheated to 80 DEG C, 2,2'- dihydroxy diethylamine, methyl caprylate and molybdenum is added into methyl caprylate
Acid is equal to 4 according to mol ratio：1,2,2'- dihydroxy diethylamine is equal to 5 with molybdic acid according to mol ratio：1, it is small that 7 are reacted at 120 DEG C
When after be cooled to 40 DEG C it is standby；2) add solvent in molybdic acid to disperse, the mass ratio of solvent and molybdenum trioxide is 3：1, then drip
The mass ratio of hydrogenation sodium hydroxide solution, sodium hydroxide and molybdic acid is 0.08：1；3) solution 2) is added to the product 1) obtained
In, 40 minutes time is added, in adding procedure, is stirred continuously, after addition, is reacted 4 hours under the conditions of being 90 DEG C in temperature；
Then reacted 2 hours under the conditions of being warming up to 110 DEG C again；After reaction terminates, obtained reaction product is subjected to extract and separate, separation
It is synthesized organic-molybdenum salt to obtain lower floor's blueness thick liquid afterwards.
Metal content analysis is carried out to product, using inductive coupling plasma emission spectrum method (analysis method GB/T
17476 equivalence margin ASTMD 5185-95), analysis result, molybdenum content is 28.5wt% in product.Dissolubility is shown in Table 2.Gained
The infrared spectrum of product is shown in Fig. 2.As it is clear from fig. 2 that in 3300-3500cm-1Nearby there are N-H stretching vibration peak, 1650cm-1It is attached
The nearly deformation vibration bands of a spectrum for having N-H, in 930cm-1、840cm-1Nearby there is Mo (O) absworption peak.
Comparative example 1
1) methyl caprylate is preheated to 80 DEG C, 2,2'- dihydroxy diethylamine, methyl caprylate and molybdenum is added into methyl caprylate
Acid is equal to 5 according to mol ratio：1,2,2'- dihydroxy diethylamine is equal to 5 with molybdic acid according to mol ratio：1, it is small that 7 are reacted at 130 DEG C
When；2) sodium hydroxide solution will be added dropwise in molybdic acid, solution temperature is 50 DEG C, is dissolved scattered complete；3) solution 2) is added to
1) in the product obtained, 40 minutes time is added, in adding procedure, is stirred continuously, is 120 DEG C of bars in temperature after addition
Reacted 3 hours under part；Then reacted 3 hours under the conditions of being cooled to 90 DEG C again；After reaction terminates, there is solid phase and sunk in reaction bottom
Product.
Metal content analysis is carried out to product, analysis result, molybdenum content is 5.7wt% in product.Dissolubility is shown in Table 2.
Embodiment 3
The residual oil property used in embodiment 3 is shown in Table 1.350g residual oil is weighed, 500 μ gg are added after being preheated to 90 DEG C-1's
Emulsifying agent, 200 μ gg are then added dropwise-1Embodiment 1 prepare organic-molybdenum salting liquid, be stirred continuously, drip during dropwise addition
It is dispersed with stirring 30 minutes after finishing, adds sodium sulfide solution, is warming up to 110 DEG C and stirs 40 minutes, then heat to 150 DEG C of gas
Removing moisture is carried, carries out hydrogenation reaction under 430 DEG C of reaction temperature, reactive hydrogen first pressing 9MPa, reaction time 1h after presulfurization, instead
Product after answering passes through standard test method (the analysis method ASTM D5307) survey that gas chromatography determines crude oil boiling Range Distribution Analysis
Product distribution is shown in Table 3 after fixed reaction.
Embodiment 4
The residual oil property used in embodiment 4 is shown in Table 1.350g residual oil is weighed, 500 μ gg are added after being preheated to 90 DEG C-1's
Emulsifying agent, 200 μ gg are then added dropwise-1Embodiment 2 in the water-soluble organic-molybdenum salting liquid for preparing, constantly stirred during dropwise addition
Mix, be dispersed with stirring after being added dropwise 30 minutes, add sodium sulfide solution, be warming up to 110 DEG C and stir 40 minutes, then heat up
Moisture are removed to 150 DEG C of air lifts, in 430 DEG C of reaction temperature after presulfurization, reactive hydrogen first pressing 9MPa, the reaction time 1 is small to enter at present
Row hydrogenation reaction, product, which is distributed, after reacted product measure reaction is shown in Table 3.
Comparative example 2
The residual oil raw material used in comparative example 2 is the same as embodiment 4.Reaction condition with embodiment 4, then adds 200 μ g
g-1Ammonium paramolybdate, after the measure reaction of reacted product product distribution is shown in Table 3.
The residual oil property of table 1
| Project | Residual oil |
| Density (20 DEG C), gcm-3 | 1.0287 |
| C content, wt% | 84.03 |
| H content, wt% | 10.01 |
| NH/NC | 1.43 |
| S contents, wt% | 4.8 |
| N content, wt% | 0.36 |
| Carbon residue, wt% | 23.2 |
| Ash content, wt% | 0.068 |
| Four components, wt% | |
| Saturation point | 9.6 |
| Fragrance point | 52.7 |
| Colloid | 24.8 |
| Asphalitine | 12.9 |
| Ni contents, μ gg-1 | 51 |
| V content, μ gg-1 | 103 |
| Boiling range, DEG C | |
| Initial boiling point, DEG C | 476 |
| 5%, DEG C | 517 |
The 2-in-1 dissolubility into organic-molybdenum of table
| Implement numbering | Mass fraction/% of the molybdenum in water | Dissolubility in water | Outward appearance |
| Embodiment 1 | 10 | It is completely dissolved | Blue thick liquid |
| Embodiment 2 | 5 | It is completely dissolved | Blue thick liquid |
| Comparative example 1 | 5 | It can not be completely dissolved | Pewter solidliquid mixture |
Product characteristicses after the hydrogenation reaction of table 3
| Product is distributed | Embodiment 3 | Embodiment 4 | Comparative example 2 |
| Gas, wt% | 4.95 | 4.69 | 7.68 |
| ~180 DEG C, wt% | 11.64 | 16.62 | 7.94 |
| 180~350 DEG C, wt% | 29.41 | 28.37 | 23.52 |
| 350~524 DEG C, wt% | 39.68 | 35.98 | 39.75 |
| >524 DEG C, wt% | 12.15 | 12.04 | 18.13 |
| Toluene insolubles, wt% | 2.17 | 2.3 | 2.98 |
From embodiment and table 3, water-soluble organic-molybdenum salt provided by the invention adds after presulfurization for inferior heavy oil
Hydrogen cracking reaction high conversion rate, light oil yield are high.In product distribution, yield of gasoline improves 3.70~8.68 compared with comparative example 2
Percentage point, diesel yield improves 4.85~5.89 percentage points, and toluene insolubles reduces by 0.68~0.81 percentage point.
Claims (10)
1. a kind of organic-molybdenum salt, it is characterised in that the organic-molybdenum salt is a kind of molybdenum amine complex, contains+6 valency molybdenum ions and molybdenum
The acyl group of ions binding and with the amido that alkyl is combined in described acyl group, the wherein mass fraction of molybdenum is the organic-molybdenum salt
10%~30%.
2. a kind of preparation method of organic-molybdenum salt, it is characterised in that comprise the following steps：
(1) 30~70 DEG C are cooled to after reacting C6~C18 ester and alcohol amine compound at 90 DEG C~150 DEG C；
(2) by the dissolving of sexavalence molybdenum source compound in a solvent, solvent and the mass ratio of sexavalence molybdenum source compound are (0.5~5):1,
Then alkaline solution is added, alkali and the mass ratio of sexavalence molybdenum source compound are (0.01~0.1)：1, described solvent is benzene, first
Benzene, water, ethanol or petroleum ether；
(3) solution of step (2) is added in step (1) reacted solution, it is anti-under the conditions of being 50~100 DEG C in temperature
Should, reacted under the conditions of being then warming up to 100~150 DEG C again；
(4) reaction product is subjected to extract and separate, it is organic-molybdenum salt that lower floor's liquid is obtained after separation.
3. according to the preparation method of the organic-molybdenum salt described in claim 2, it is characterised in that C6~C18 in the step (1)
Ester and the mol ratio of sexavalence molybdenum source compound are (2~8)：1；The mol ratio of alcohol amine compound and sexavalence molybdenum source compound for (2~
8)：1；Solvent and the mass ratio of sexavalence molybdenum source compound are (0.5~4) in step (2)：1.
4. according to the preparation method of the organic-molybdenum salt described in claim 2, it is characterised in that described C6~C18 ester is selected from
Butyl acetate, methyl caprylate, amyl acetate, amyl valerate, ethyl butyrate, isoamyl acetate, cognac oil, methyl valerate, oneself
One or more in sour pentyl ester, ethyl caprilate and ethyl valerate.
5. according to the preparation method of the organic-molybdenum salt described in claim 2, it is characterised in that described alcohol amine compound is selected from two
Monoethanolamine, triethanolamine, monoethanolamine, diethyl ethylene diamine, Diethylaminoethanol amine, dibutylamino ethanol, isopropanolamine, hydroxyl
One or more in ethamine, ethylaminoethanol, dibutylamino ethanol and dialkyl group isopropanolamine.
6. according to the preparation method of the organic-molybdenum salt described in claim 2, it is characterised in that described alkaline solution is selected from carbonic acid
Sodium, sodium acid carbonate, the aqueous solution of potassium hydroxide or sodium hydroxide.
7. according to the preparation method of the organic-molybdenum salt described in claim 2, it is characterised in that described sexavalence molybdenum source compound choosing
One or more from molybdic acid, ammonium molybdate, ammonium paramolybdate and molybdenum trioxide.
8. according to the preparation method of the organic-molybdenum salt described in claim 2, it is characterised in that step (1) is at 90 DEG C~150 DEG C
Reaction 1~6 hour, is then cooled to standby at 40 DEG C -70 DEG C.
9. according to the preparation method of the organic-molybdenum salt described in claim 2, it is characterised in that step (3) is 50~100 in temperature
Reacted 2~7 hours under the conditions of DEG C；Then reacted 1~6 hour under the conditions of being warming up to 100~150 DEG C again.
10. the method for the organic-molybdenum salt catalysis residual hydrogenation described in claim 1, it is characterised in that during residual hydrogenation,
Using the organic-molybdenum salt as catalyst precursor, the mass fraction that its addition accounts for resid feed is 0.01%-0.3%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110776976A (en) * | 2019-11-07 | 2020-02-11 | 重庆昆崧科技有限公司 | Preparation method of lubricating oil extreme pressure antiwear agent |
| CN111518606A (en) * | 2020-05-27 | 2020-08-11 | 华阳新兴科技（天津）集团有限公司 | Copper foil rolling oil and preparation method and application thereof |
| CN112175690A (en) * | 2020-09-01 | 2021-01-05 | 清华大学天津高端装备研究院 | Preparation method of non-sulfur-phosphorus oil-soluble organic molybdenum additive |
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| CN1360013A (en) * | 2000-12-19 | 2002-07-24 | 邱志远 | Water-soluble extreme-pressure antiwear antifriction organomolybdenum additive |
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Cited By (7)
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| CN110776976A (en) * | 2019-11-07 | 2020-02-11 | 重庆昆崧科技有限公司 | Preparation method of lubricating oil extreme pressure antiwear agent |
| CN111518606A (en) * | 2020-05-27 | 2020-08-11 | 华阳新兴科技（天津）集团有限公司 | Copper foil rolling oil and preparation method and application thereof |
| CN111518606B (en) * | 2020-05-27 | 2022-02-22 | 华阳新兴科技（天津）集团有限公司 | Copper foil rolling oil and preparation method and application thereof |
| CN112175690A (en) * | 2020-09-01 | 2021-01-05 | 清华大学天津高端装备研究院 | Preparation method of non-sulfur-phosphorus oil-soluble organic molybdenum additive |
| CN112175690B (en) * | 2020-09-01 | 2022-04-12 | 清华大学天津高端装备研究院 | Preparation method of non-sulfur-phosphorus oil-soluble organic molybdenum additive |
| CN115722269A (en) * | 2022-11-08 | 2023-03-03 | 润和催化剂股份有限公司 | Oil-soluble dispersion type composition and preparation method and application thereof |
| CN115722269B (en) * | 2022-11-08 | 2024-02-27 | 润和催化剂股份有限公司 | Oil-soluble dispersion type composition and preparation method and application thereof |
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