CN1231943A - Heteropoly acid salt catalyst, process for producing same and its use - Google Patents
Heteropoly acid salt catalyst, process for producing same and its use Download PDFInfo
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- CN1231943A CN1231943A CN 99112863 CN99112863A CN1231943A CN 1231943 A CN1231943 A CN 1231943A CN 99112863 CN99112863 CN 99112863 CN 99112863 A CN99112863 A CN 99112863A CN 1231943 A CN1231943 A CN 1231943A
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Abstract
A catalyst of heteropoly acid's salt features that its central atom is P, its coordination atom is W, Mo, or V, its chemical formula is A6/n[P2M18O62], where A is metal ion chosen from Zn, Fe, Al, Cu and Mg, n is the number of valence of metal ion, and M is the metal chosen from W, Mo and V, the condensation ratio of two inorganic oxy-acids is 2 : 18, and it has Dawson structure. Its advantages are low cracking temp, avoiding coking and scaling, and obviously reducing viscosity of crude.
Description
The present invention proposes to protect is that a kind of new catalyst and its production technology and this catalyst carry out the catalysis visbreaking to viscous crude or super viscous crude, to obtain the application of a small amount of light oil, dry gas and fuel oil.
The reserves of underground viscous crude are very abundant, and explored reserves substantially exceed the reserves of ordinary crude oils.China, Canada, Venezuela etc. all are viscous crude big countries.Viscous crude, particularly super viscous crude, it has the density height and (approaches 1000kg/m
3), viscosity height (in the time of 50 ℃, several ten thousand-hundreds thousand of MPa.S), initial boiling point height (at 150-350 ℃ category), freezing point height (more than 30 ℃), characteristics such as colloid and asphalt content height.These characteristics give that the exploitation of viscous crude, collection are defeated, desalting and dewatering and refining processing bring sizable difficulty.It almost is impossible adopting common crude oil manufacturing process.At present, often adopt and be processed into water emulsifying oil on the spot, oil acts as a fuel.But the stability of water emulsifying oil is difficult to control, is easy to breakdown of emulsion between the storage life, and simultaneously, Combustion of Emulsified Oil heat descends greatly, and the user generally is unwilling to accept.
In modern petroleum refining industry, catalytic cracking is most important heavy oil residue manufacturing process, and its adopts Y zeolite as catalyst, riser reactor, and reaction temperature is greatly about about 800K, and the time of contact of catalyst and oil is greatly about 2-4 second.The regeneration of catalyst is carried out at fluid bed.Deliver to the fractionation part after crackate and the catalyst separation.Visbreaking is a mature technology in the petroleum refining industry, as far back as the beginning of this century, just makes the C-C key be subjected to thermal destruction whereby, to improve the productive rate of gasoline, then is mainly catalytic cracking now and supplies raw materials, and is called visbreaking.Viscous crude, particularly super viscous crude, because high viscosity and high-solidification point can use visbreaking that its viscosity is reduced, still, the temperature of visbreaking can not be too high, otherwise very easily cause coking and fouling, is difficult to long-term operation.Can avoid coking and fouling though temperature is low, cracking level is very shallow, and viscosity does not reach requirement.
The purpose of this invention is to provide a kind of novel catalyst, its production technology and the application in viscous crude or super viscous crude catalysis visbreaking process thereof, it can make the cracking temperature reduce, avoid coking and fouling, and the visbreaking production technology of viscous crude and super viscous crude is simplified.
The object of the present invention is achieved like this: catalyst of the present invention is different from the Y zeolite in the catalytic cracking process fully, it is a kind of heteropolyacid salt, water-soluble, mixing together enters cracker with crude oil, crackate does not separate with catalyst, on technology, be a kind of transformation to traditional viscosity breaking technology, we are called the catalysis visbreaking.Catalyst of the present invention has following composition, and its central atom is P, and coordination atom is W, Mo, and V etc., chemical formula are A
6/n[P
2M
18O
62], wherein, A is Zn, Fe, and Al, Cu, metal ions such as Mg, n are the valence mumbers of metal ion, M represents W, Mo, metals such as V, the condensation ratio of two kinds of inorganic oxacids is 2: 18, has the Dawson structure.
The production technology of above-mentioned catalyst is: technology is produced tungsten (or molybdenum or vanadium) phosphoric acid of Dawson structure and soluble in water at first routinely, and molten 2g in every ml water gets ZnCl
2(or FeCl
3, or AlCl
3.6H
2O) soluble in water in right amount, it is dropwise joined in tungsten (or molybdenum or vanadium) phosphoric acid solution, the while vigorous stirring, placement is spent the night, and the recrystallization secondary promptly gets heteropolyacid salt catalyst of the present invention.
The great advantage of heteropolyacid salt catalyst of the present invention is that the temperature of cracking is reduced, and avoids coking and fouling.As shown in Figure 1, in the time of 345 ℃, the beginning cracking, 395 ℃ is the maximum temperature of cracking reaction, the temperature range of cracking reaction is at 345-473 ℃.In fact be that cracking reaction is carried out the fiercest interval between 395-473 ℃, in actual moving process, this is the big and coking fouling district of cracking level, and temperature is in case surpass 473 ℃, and crude oil is with all coking.Therefore, cracking reaction will be controlled between 345-395 ℃, to avoid coking.Fig. 2 is the thermogravimetric analysis figure of the crude oil behind the interpolation heteropolyacid salt catalyst, and we find that 345 ℃ peak disappears, and widen greatly in the interval of cracking reaction, and about 285 ℃ of beginnings, maximum temperature is at 399 ℃ greatly.Therefore, cracking reaction is controlled between 350-380 ℃, the degree of depth of control visbreaking, long-term operation safely.
Heteropolyacid salt catalyst of the present invention has water-soluble.As everybody knows, the dehydration of super viscous crude is difficulty very, general residual water is always at 5-10%, and heteropolyacid salt is water-soluble, with the ionic species homogeneous catalysis, needn't separate and regenerate after reaction is carried out, when visbreaking oil acts as a fuel the oil use, remaining metal ion is harmless, and this simplifies technology greatly, and this is second advantage of the present invention.
It is believed that now, in viscous crude and the super viscous crude, colloid and asphalitine are that the form with micella exists, micella is tens of or up to a hundred colloids or asphaltene molecules are formed, molecular weight is very big, and it is the main cause that causes viscosity of crude to increase, and so-called visbreaking is exactly the C-C key that ruptures in fact, big molecule is diminished, reduce viscosity.Colloid or asphaltene molecules are the condensed nucleus aromatic compounds, and visbreaking can not opened aromatic rings, and the outer side chain of aromatic rings only may rupture.The maximum characteristics of heteropolyacid salt catalyst of the present invention are after adding crude oil, the viscosity of crude oil just can significantly reduce, through our Primary Study, possible reason is, it weakens the molecular separating force that forms micella, and micella nuclear is diminished, and has reduced the viscosity of viscous crude, this is significant to the interaction force between research colloid or asphaltene molecules, also is of the present invention one big advantage.
Studies show that in recent years, be difficult to the water sloughed in the viscous crude, be a kind of composition (J.Petroleum Geology, 5,1983 of viscous crude cracking reaction in fact with catalytic action, 363), organosulfur compound is a component the most responsive in the heavy oil with regard to hydrothermal cracking, the reaction of high-temperature water and organosulfur compound, may discharge or not discharge H with the hydrolysed form of sulphur-carbon bond
2S, the steam displacement produces a certain amount of hydrogen, that is to say, has hydro-upgrading to take place in the steam cracking process.Ion Zn in the heteropolyacid salt catalyst of the present invention
2+, Fe
3+, Al
3+Plasma; Or heteropolyacid anions; Or the Ni in the oil composition, V, or the like can both the catalysis hydrothermal cracking reaction, might be combining by metal ion and sulphur atom, thereby activated binding site and hydrone is had an effect, metal ion hydrolysis well, this helps hydrone is taken to the position of reaction.Therefore, in the place of production of viscous crude and super viscous crude it is carried out the catalysis visbreaking, less demanding to what dewater, this is very favorable on technology.
Because the dosage of heteropolyacid salt is very low, greatly about 100-500ppm, therefore, it can not make processing cost increase significantly, and this is another advantage of the present invention.
Therefore, adopting catalyst of the present invention, viscous crude and super viscous crude are carried out catalysis visbreaking on the spot, is splendid means that solve viscous crude and the processing of super viscous crude.
The present invention is further detailed explanation below in conjunction with embodiment and accompanying drawing.
Embodiment one
200 gram Na
2WO
4.2H
2O is dissolved in the 1L deionized water, adds 85% phosphoric acid 280 grams, and agitating heating refluxed 8 hours in there-necked flask, and solution concentration adds the product oxidation that several bromine waters make partial reduction to 1L, and it is light yellow that solution is, and adds the Powdered NH of 200 grams after the cooling while stirring
4Cl obtains light yellow crystal (repetition secondary) with the Buchner funnel suction filtration.Dissolve being deposited in 600 milliliters 50 ℃ the water, in 37 ℃ of water-baths, leave standstill a couple of days to separate out flaxen crystal (NH
4)
6P
2W
18O
62, be recrystallized again 2 times.
Get 50 gram ammonium tungstophosphates and be dissolved in 100 ml waters, add 60 milliliters of concentrated hydrochloric acids, use extracted with diethyl ether, tell lower floor's yellow liquid, add 20 ml waters air stripping ether, place the drier drying of finding time, separate out yellow tungstophosphoric acid, molecular formula is H
6P
2W
18O
62.14H
2O.This is a kind of tungstophosphoric acid of the Dawson of having structure.
Get 50 grams and be H
6P
2W
18O
6214H
2O adds the dissolving of 25 ml waters, 4 gram ZnCl
2Add the dissolving of 20 ml waters, with ZnCl
2Solution dropwise is added in the tungstophosphoric acid solution, and at this moment vigorous stirring has many crystal to separate out simultaneously, and placement is spent the night, and the recrystallization secondary gets Zn
3P
2W
18O
6214H
2O is as the catalyst of super viscous crude catalysis visbreaking.
The experiment of super viscous crude catalysis visbreaking is carried out in autoclave, and extraction catheter connects condenser pipe on the kettle cover, collects light component.Cracking gas is collected by draining water gathering of gas law.Crude oil comes to Chinese Liaohe Oil Field Du's-84 blocks, water content 8%, and other rerum natura sees the following form:
Experiment condition:
Sequence number | Analysis project | Analysis result | |
?1 | Density g/cm, 20 ℃ | ????0.9849 | |
?2 | Kinematic viscosity mPa/s | ?80℃ | ????2687.55 |
?100℃ | ????1757.9 | ||
?3 | Condensation point ℃ | ????28 | |
?4 | Flash-point ℃ | ????137 | |
?5 | Moisture | Trace | |
?6 | Sulphur % | ????0.32 | |
?7 | Nitrogen % | ????0.31 | |
?8 | Ash content % | ????0.17 | |
?9 | Colloid % | ????23.9 | |
?10 | Asphalitine % | ????3.3 | |
?11 | Wax content % | ????0.7 | |
?12 | ????Fe?ppm | ????125.59 | |
?13 | ????Ni?ppm | ????228.17 | |
?14 | ????Cu?ppm | ????0.78 | |
?15 | ????Na?ppm | ????8804 |
Pressure: normal pressure; Temperature: 380 ℃; 400 ℃, raw material: 150-200g;
Speed of agitator: 120-180 rev/min; Programming rate: 6 ℃/minute; Reaction time: 2 hours.
Reactor volume: 500 milliliters.
The Zn that adds 100ppm in the feedstock oil
3Cl
2P
2W
18O
6214H
2O enters that the speed with 6 ℃/minute heats up behind the reactor, and when rising to 150 ℃, beginning is with 120-180 rev/min of stirring, reach 350 ℃ after, with 3 ℃ of/minute intensification, reach reaction temperature after, control constant temperature 2 hours, cooling then, survey gas, light oil, the yield of visbreaking viscous crude.And the viscosity of survey visbreaking viscous crude.Check that the reactor wall has or not coking phenomenon, if its content of mensuration is arranged.
Under same experimental conditions, the heat scission reaction of crude oil when all having carried out not adding catalyst is with as a comparison.Experimental result please see the following form:
Embodiment two
Project | Cracking gas % | Light oil yield % | Visbreaking oil yield % | 80 ℃ of mPa/s of | 100 ℃ of mPa/s of visbreaking oil viscosity |
380 ℃ of hot visbreakings | ????2.1 | ????7.8 | ????90.1 | ????1028 | ????295 |
400 ℃ of hot visbreakings | ????2.8 | ????17.1 | ????80.1 | ????1027 | ????293 |
380 ℃ of catalysis visbreakings | ????2.4 | ????17.6 | ????80.0 | ????840 | ????250 |
400 ℃ of catalysis visbreakings | ????3.4 | ????28.8 | ????67.8 | ????915 | ????180 |
Produce H by said method among the embodiment one
6P
2W
18O
6214H
2O.Get 50 gram H
6P
2W
18O
6214H
2O adds the dissolving of 25 ml waters, 2.5 gram FeCl
3Add the dissolving of 20 ml waters, with FeCl
3Solution dropwise is added in the tungstophosphoric acid solution, and at this moment vigorous stirring has many crystal to separate out simultaneously, and placement is spent the night, and the recrystallization secondary gets Fe
2P
2W
18O
6214H
2O is as the catalyst of super viscous crude catalysis visbreaking.Experimental technique and raw material are with embodiment one, and result of the test sees the following form:
Embodiment three
Project | Cracking gas % | Light oil yield % | Visbreaking oil yield % | 80 ℃ of mPa/s of | 100 ℃ of mPa/s of visbreaking oil viscosity |
380 ℃ of hot visbreakings | ????2.1 | ????7.8 | ????90.1 | ????1028 | ????295 |
400 ℃ of hot visbreakings | ????2.8 | ????17.1 | ????80.1 | ????1027 | ????293 |
380 ℃ of catalysis visbreakings | ????3.4 | ????18.6 | ????78.0 | ????894 | ????267 |
400 ℃ of catalysis visbreakings | ????3.7 | ????29.3 | ????67.0 | ????975 | ????198 |
Produce H by said method among the embodiment one
6P
2W
18O
6214H
2O.Get 50 gram H
6P
2W
18O
6214H
2O adds the dissolving of 25 ml waters, 11 gram AlCl
36H
2O adds the dissolving of 25 ml waters, with AlCl
3Solution dropwise is added in the tungstophosphoric acid solution, and at this moment vigorous stirring has many crystal to separate out simultaneously, and placement is spent the night, and the recrystallization secondary gets Al
2P
2W
18O
6214H
2O is as the catalyst of super viscous crude catalysis visbreaking.Experimental technique and raw material are with embodiment one, and result of the test sees the following form.
Project | Cracking gas % | Light oil yield % | Visbreaking oil yield % | 80 ℃ of mPa/s of | 100 ℃ of mPa/s of visbreaking oil viscosity |
380 ℃ of hot visbreakings | ????2.1 | ????7.8 | ????90.1 | ????1028 | ????295 |
400 ℃ of hot visbreakings | ????2.8 | ????17.1 | ????80.1 | ????1027 | ????293 |
380 ℃ of catalysis visbreakings | ????2.6 | ????15.4 | ????82.0 | ????914 | ????277 |
400 ℃ of catalysis visbreakings | ????3.0 | ????27.3 | ????69.7 | ????1015 | ????298 |
At any change and the variation that the present invention did,, must understand that then this change and variation are included within protection scope of the present invention as if being conspicuous for the professional and technical personnel.
Claims (3)
1, a kind of heteropolyacid salt catalyst is characterized in that this catalyst has following composition, and its central atom is P, and coordination atom is W, Mo, and V etc., chemical formula are A
6/n[P
2M
18O
62], wherein, A is Zn, Fe, and Al, Cu, Mg waits metal ion, and n is the valence mumber of metal ion, and M represents W, Mo, metals such as V, the condensation ratio of two kinds of inorganic oxacids is 2: 18, has the Dawson structure.
2, as the production technology of the said heteropolyacid salt of claim 1, technology is produced tungsten (or molybdenum or vanadium) phosphoric acid of Dawson structure and soluble in water at first routinely, and molten 2g in every ml water gets ZnCl
2(or FeCl
3, or AlCl
3.6H
2O) soluble in water in right amount, it is dropwise joined in tungsten (or molybdenum or vanadium) phosphoric acid solution, the while vigorous stirring, placement is spent the night, and the recrystallization secondary promptly gets heteropolyacid salt catalyst of the present invention.
3, as the application of the said heteropolyacid salt catalyst of claim 1 in viscous crude or the production of super viscous crude catalysis visbreaking, it is characterized in that reaction condition is: 300 ℃-400 ℃ of temperature, the reaction pressure normal pressure, catalyst addition 100-500ppm, reaction time 2-3 hour.
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CN99112863A CN1089037C (en) | 1999-04-20 | 1999-04-20 | Heteropoly acid salt catalyst, process for producing same and its use |
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CN99112863A CN1089037C (en) | 1999-04-20 | 1999-04-20 | Heteropoly acid salt catalyst, process for producing same and its use |
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CN1089037C CN1089037C (en) | 2002-08-14 |
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Family Cites Families (5)
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US3825488A (en) * | 1973-05-07 | 1974-07-23 | Universal Oil Prod Co | Process for hydrorefining a hydrocarbon charge stock |
US4607122A (en) * | 1981-04-27 | 1986-08-19 | Atlantic Richfield Company | High selectivity process for vapor phase oxydehydrogenation of alkanoic acids, such as isobutyric acid, using Dawson structure phosphomolybdic acid |
CA1305467C (en) * | 1986-12-12 | 1992-07-21 | Nobumitsu Ohtake | Additive for the hydroconversion of a heavy hydrocarbon oil |
DE4424625A1 (en) * | 1994-07-13 | 1996-01-18 | Degussa | Microporous hetero:poly:oxo:metallate(s) useful as shape-selective catalysts |
CN1048654C (en) * | 1994-12-22 | 2000-01-26 | 吉林大学 | Dawson-structure heteropoly compound catalyst for synthesizing hydrochinone with phenol and hydrogen peroxide by hydroxylation and its preparation |
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1999
- 1999-04-20 CN CN99112863A patent/CN1089037C/en not_active Expired - Fee Related
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