CN102311756B - Addition agent for thermal inversion process of heavy oil and preparation method of addition agent - Google Patents
Addition agent for thermal inversion process of heavy oil and preparation method of addition agent Download PDFInfo
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- CN102311756B CN102311756B CN2010102115590A CN201010211559A CN102311756B CN 102311756 B CN102311756 B CN 102311756B CN 2010102115590 A CN2010102115590 A CN 2010102115590A CN 201010211559 A CN201010211559 A CN 201010211559A CN 102311756 B CN102311756 B CN 102311756B
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Abstract
The invention relates to an addition agent for a thermal inversion process of heavy oil and a preparation method of the addition agent. The addition agent contains 5-15% of acidified inorganic material, 5-15% of oil-soluble free radical initiator and 70-90% of dispersant; the acidified inorganic material is obtained by treating the inorganic material the Al2O3 mass content of which is not less than 15% by utilizing an inorganic strong acid solution, then drying, baking and crushing; the average grain diameter of the acidified inorganic material is not more than 300 microns; and the viscosity of the dispersant at 100 DEG C is not less than 30 mm<2>/s. According to the addition agent provided by the invention, the liquid product yield in the thermal inversion process of the heavy oil is improved and the yield of coke is reduced.
Description
Technical field
The present invention relates to a kind of auxiliary agent for the heavy oil thermal conversion process and preparation method thereof, specifically, is a kind of be used to auxiliary agent of improving heavy oil thermal conversion process liquid product yield and preparation method thereof.
Background technology
Along with a large amount of consumption of light crude, the heaviness trend of world petroleum resource is constantly aggravated, and the demand of light-end products increases day by day, so the upgrading of heavy oil and deep processing become one of important topic that Petrochemical Enterprises faces.Heavy oil mainly refers to density>0.93g/cm
3Crude oil and the residual oil of boiling point>350 ℃, usually also comprise shale oil, oil-sand wet goods resource.Thermal conversion processes is that to make heavy oil conversion be the technological process of gas, light oil, oil fuel or coke by improving temperature under the on-catalytic condition, and viscosity breaking and coking are topmost two class thermal conversion processess wherein.
In various coking process, delayed coking is current most widely used technology, and the delayed coking treatment capacity of China has reached 8.5Mt/a at present.The liquid yield of delay coking process, can be lower during the processing poor residuum in 70% left and right, and coke yield can reach 30%, is the major objective of this technique so improve the coking liquid product yield.It is a kind of effective way that improves production efficiency of delayed coking liquid product that interpolation has the auxiliary agent that increases the liquid effect, the Main Function of auxiliary agent: the one, and promote free radical to generate, increase the cracking level of raw material; The 2nd, stop the free radical condensation, reduce the probability of macromolecular radical condensation coking.As Texaco company, proposing in the delayed coking charging, to add massfraction is the traditional radical initiator of chain reaction delivery agent (as mercaptan, tetracol phenixin etc.) and 0.1% left and right of 0.5% left and right, the Mobil oil company proposes to add free radical terminator in the delayed coking charging, and purpose is all to reduce the further condensation of unstable hydrocarbon type free base that thermally splitting produces.In addition, also there are some documents to propose low-carbon alkene, tensio-active agent or defoamer and the composite auxiliary agent of scorch retarder.
Summary of the invention
The invention provides a kind of auxiliary agent for the heavy oil thermal conversion process and preparation method thereof, this auxiliary agent can improve the liquid product yield of heavy oil thermal conversion process, the productive rate of reduction coke.
A kind of auxiliary agent for the heavy oil thermal conversion process, the quality of auxiliary agent of take is benchmark, contains 5%～15% acidifying inorganic materials, 5%～15% oil soluble radical initiator and 70%～90% dispersion agent; Described acidifying inorganic materials is to process Al with the inorganic acid aqueous solution
2O
3The inorganic materials of mass content>=15%, and drying, roasting, pulverizing and obtain the median size of acidifying inorganic materials≤300 μ m; Described dispersion agent is at the viscosity>=30mm of 100 ℃
2/ s.
In described inorganic materials, Al
2O
3Mass content preferably>=30%, more preferably>=40%.Described inorganic materials can be one or more in aluminium hydroxide, aluminum oxide, clay, zeolite and aluminate, is preferably one or more in pseudo-boehmite, gama-alumina, calcium aluminate, y-type zeolite, kaolin and polynite.
The median size of described acidifying inorganic materials preferably≤100 μ m.Median size in the present invention is the linear averaging particle diameter, adopts the sedimentation particle size analyzer determination.
Described inorganic acid can be hydroiodic acid HI, perchloric acid, Hydrogen bromide, hydrochloric acid, nitric acid or sulfuric acid, is preferably hydrochloric acid, nitric acid or sulfuric acid.
Described oil soluble radical initiator is preferably one or more of alkyl peroxide, alkyl peroxide and peroxyester.
The viscosity upper limit of dispersion agent is relevant with the stock oil of heavy oil thermal conversion process, as basic general knowledge, can better be scattered in stock oil in order to make auxiliary agent, and the viscosity of dispersion agent should be less than the raw material oil viscosity.In described dispersion agent, the total content of naphthenic hydrocarbon and light aromatic hydrocarbons preferably >=50m%, wherein light aromatic hydrocarbons refers to monocycle, dicyclo and thrcylic aromatic hydrocarbon.Described dispersion agent is preferably naphthane, 9,10-dihydroanthracene, 9,10-dihydro phenanthrene, methylnaphthalene, lube oil finishing oil, catalytically cracked oil etc.In preferred embodiments of the present invention, use the dispersion agent that is rich in naphthenic hydrocarbon and light aromatic hydrocarbons, can stop on the one hand the polymerization of aromatic hydrocarbons macromole to generate coke precursor, thereby reduce the productive rate of coke, can promote heat cracking reaction on the other hand.
The preparation method of above-mentioned auxiliary agent comprises:
(1) in the inorganic acid aqueous solution, process inorganic materials, separate drying, roasting;
(2) sample step (1) obtained is crushed to median size≤300 μ m;
(3) sample dispersion step (2) obtained is in the dispersion agent that contains the oil soluble radical initiator.
In preferred situation, front in step (1), by described inorganic materials roasting 4h at least between 400～650 ℃.
In step (1), described inorganic acid is hydroiodic acid HI, perchloric acid, Hydrogen bromide, hydrochloric acid, nitric acid or sulfuric acid, and the concentration of the inorganic acid aqueous solution is 1～5mol/L, is preferably 1～3mol/L; The acid treatment time is 0.5～4h preferably, and treatment temp is preferably 60～90 ℃; Drying temperature is preferably 100～120 ℃, is preferably 4～12h time of drying; Preferably 400～650 ℃ of maturing temperatures, roasting time is 4～8h preferably.
In step (2), the sample preferably step (1) obtained is crushed to median size≤100 μ m.
In step (3), preferably adopt the mode of high-speed stirring, the sample dispersion that step (2) is obtained is in the dispersion agent that contains the oil soluble radical initiator.By the method that high-speed stirring is disperseed, belong to prior art.
The applicable thermal conversion processes of auxiliary agent of the present invention, include but not limited to viscosity breaking, delayed coking, flexicoking and fluid coking.
The present invention makes and increases the liquid auxiliary agent with acidifying inorganic materials, oil soluble radical initiator and dispersion agent, and this auxiliary agent has well but Jiao increases the fluidity energy.This auxiliary agent that adds 200 μ g/g～0.1% in the delayed coking reaction feed stream, coke yield descends 2～5 percentage points under the same process condition, and liquid product yield increases by 2～4 percentage points.
Embodiment
Further set forth by the following examples the present invention.
Embodiment 1
Get the kaolin of 50g at 550 ℃ of roasting 4h, at 70 ℃, process 2h with the HCl of 1mol/L, then at 120 ℃ of dry 4h, 550 ℃ of roasting 4h, obtain the acid-treated kaolin of salt, is crushed into 120 orders (120 μ m) standby, is designated as A-1.
By A-1: dicumyl peroxide (DCP): the mass ratio of naphthane=5: 5: 90 mixes the three, at 800rpm, stirs 30min and obtains auxiliary agent A.
The benchmark test of auxiliary agent carries out on the static heat conversion system in laboratory, (quality of stock oil of take is benchmark in reactor, to add a certain amount of stock oil first (character is in Table 1) and auxiliary agent A, add-on is 200 μ g/g), then rise to 470 ℃ of temperature of reaction, stop 30min.Crackate liquid product after cooling enters holding tank, and gaseous product is through the gas meter metering volume, and sedimentation of coke is at reactor bottom, and test-results is in Table 2.
As can be seen from Table 2,470 ℃, add the auxiliary agent A of 200 μ g/g, liquid product yield is 64.67%, improves 0.8 percentage point than Comparative Examples 1; Coke yield is 26.28%, compares ratio 1 and descends 1 percentage point.
Comparative Examples 1
Comparative Examples 1 is not added any auxiliary agent, adopts reaction conditions and the raw material identical with embodiment 1, and test-results is in Table 2.
As can be seen from Table 2, do not add any auxiliary agent, at 470 ℃, the coke yield of stock oil is 27.28%, and liquid product yield is 63.87%.
Embodiment 2
Get γ-Al of 50g
2O
3, with the H of 2mol/L
2SO
4At 80 ℃, process 2h, at 120 ℃ of dry 4h, 550 ℃ of roasting 4h, obtain the gama-alumina of vitriolization, is crushed into 120 orders (120 μ m) standby, is designated as B-1.
B-1 in mass ratio: radical initiator dibenzoyl peroxide (BPO): the mass ratio of 9,10-dihydroanthracene=5: 10: 85 mixes the three, first at 800rpm, stirs 30min, obtains auxiliary agent B.
In the stock oil first, add auxiliary agent B, the quality of stock oil of take is benchmark, and add-on is 500 μ g/g, and reaction conditions is with embodiment 1, and test-results is listed in table 2.As can be seen from Table 2, compare with Comparative Examples 1, liquid product yield improves 0.9 percentage point, reaches 64.77%; Coke yield descends 1.2 percentage points, reaches 26.08%.
Embodiment 3
Get the illiteracy holder soil of 50g, with the H of 2mol/L
2SO
4At 80 ℃, process 2h, at 120 ℃ of dry 4h, 550 ℃ of roasting 4h, obtain the illiteracy holder soil of vitriolization, be crushed into 150 orders (100 μ m) standby, be designated as C-1;
Press C-1: ditertiary butyl peroxide (DTBP): 9,10-dihydro is luxuriant and rich with fragrance=and the mass ratio of 10: 5: 85 mixes the three, stirs 20min at 1000rpm, obtains auxiliary agent C.
In the stock oil first, add auxiliary agent C, the quality of stock oil of take is benchmark, and add-on is 1000 μ g/g, and reaction conditions is with embodiment 1, and test-results is in Table 2.
As can be seen from Table 2, compare with Comparative Examples 1, add the auxiliary agent C of 1000 μ g/g, the productive rate of coke is 25.28%, has descended 2 percentage points, and liquid product yield increases by 1.6 percentage points, increases to 64.47%.
Embodiment 4
Get the Y molecular sieve of 50g, with the HNO of 3mol/L
3At 70 ℃, process 2h, at 120 ℃ of dry 4h, 550 ℃ of roasting 4h, obtain the Y molecular sieve of nitric acid treatment, is crushed into 200 orders (70 μ m) standby, is designated as D-1.
By D-1: ditertiary butyl peroxide (DTBP): the mass ratio of lube oil finishing oil=15: 5: 80 mixes the three, stirs 30min at 800rpm, obtains auxiliary agent D.In lube oil finishing oil, the mass content sum of naphthenic hydrocarbon and light aromatic hydrocarbons is 63%.
In the stock oil first, add auxiliary agent D, the quality of stock oil of take is benchmark, and add-on is 3000 μ g/g, and reaction conditions is with embodiment 1, and test-results is in Table 2.
As can be seen from Table 2, adding the productive rate of 3000 μ g/g auxiliary agent D coke is 22.78, has descended 4.5 percentage points than Comparative Examples 1, and liquid product yield is 67.87%, increases by 4 percentage points than Comparative Examples 1.
Embodiment 5
Get the baked kaolin of 50g, with the HNO of 2mol/L
3At 70 ℃, process 2h, at 120 ℃ of dry 4h, 550 ℃ of roasting 4h, obtain the kaolin of nitric acid treatment, is crushed into 150 orders (100 μ m) standby, is designated as E-1.
By E-1: ditertiary butyl peroxide (DTBP): the mass ratio of catalytically cracked oil=5: 15: 80 mixes the three, first at 800rpm, stirs 30min, obtains auxiliary agent E.The mass content sum of the naphthenic hydrocarbon in catalytically cracked oil and light aromatic hydrocarbons is 70%.
In the stock oil first, add auxiliary agent E, the quality of stock oil of take is benchmark, and add-on is 3000 μ g/g, and reaction conditions is with embodiment 1, and test-results is in Table 2.
As can be seen from Table 2, add 3000 μ g/g auxiliary agent E, the productive rate of coke descends 1.5 percentage points, and liquid product yield increases by 1.15 percentage points.
Embodiment 6
In raw material second (character is in Table 1), add auxiliary agent D, the quality of stock oil of take is benchmark, and add-on is 5000 μ g/g, 490 ℃ of temperature of reaction, and test-results is in Table 3.
As can be seen from Table 3, the coke yield of raw material second is 24.68%, relatively descends 3.9 percentage points with Comparative Examples 2, and liquid product yield is 65.95%, improves 3.28 percentage points than Comparative Examples 2.
Comparative Examples 2
Comparative Examples 2 is not added any auxiliary agent, adopts reaction conditions and the raw material identical with embodiment 5, and test-results is in Table 3.
As can be seen from Table 3, do not add any auxiliary agent, at 490 ℃, the coke yield of stock oil is 28.58%, and liquid product yield is 62.67%.
Table 1
Table 2
Table 3
Claims (15)
1. auxiliary agent for the heavy oil thermal conversion process, the quality of auxiliary agent of take is benchmark, contains 5%～15% acidifying inorganic materials, 5%～15% oil soluble radical initiator and 70%～90% dispersion agent; Described acidifying inorganic materials is to process Al with the inorganic acid aqueous solution
2O
3The inorganic materials of mass content>=15%, and drying, roasting, pulverizing and obtain the median size of acidifying inorganic materials≤300 μ m; Described dispersion agent is at the viscosity>=30mm of 100 ℃
2/ s.
2. according to auxiliary agent claimed in claim 1, it is characterized in that, described inorganic materials is one or more in aluminium hydroxide, aluminum oxide, clay, zeolite and aluminate.
3. according to auxiliary agent claimed in claim 2, it is characterized in that, described inorganic materials is one or more in pseudo-boehmite, gama-alumina, calcium aluminate, y-type zeolite, kaolin and polynite.
4. according to auxiliary agent claimed in claim 1, it is characterized in that the median size of described acidifying inorganic materials≤100 μ m.
5. according to auxiliary agent claimed in claim 1, it is characterized in that, described inorganic acid is hydroiodic acid HI, perchloric acid, Hydrogen bromide, hydrochloric acid, nitric acid or sulfuric acid.
6. according to auxiliary agent claimed in claim 1, it is characterized in that, described oil soluble radical initiator is one or more of alkyl peroxide and peroxyester.
7. according to auxiliary agent claimed in claim 1, it is characterized in that, in described dispersion agent, the total content >=50m% of naphthenic hydrocarbon and light aromatic hydrocarbons.
8. according to auxiliary agent claimed in claim 7, it is characterized in that, described dispersion agent is naphthane, 9,10-dihydroanthracene, 9,10-dihydro phenanthrene, methylnaphthalene, lube oil finishing oil or catalytically cracked oil.
9. the preparation method of the described auxiliary agent of claim 1 comprises:
(1) in the inorganic acid aqueous solution, process inorganic materials, separate drying, roasting;
(2) sample step (1) obtained is crushed to median size≤300 μ m;
(3) sample dispersion step (2) obtained is in the dispersion agent that contains the oil soluble radical initiator.
10. in accordance with the method for claim 9, it is characterized in that, described inorganic acid is hydroiodic acid HI, perchloric acid, Hydrogen bromide, hydrochloric acid, nitric acid or sulfuric acid, and the concentration of the inorganic acid aqueous solution is 1～5mol/L.
11. in accordance with the method for claim 9, it is characterized in that, in step (1), acid treatment time 0.5～4h, treatment temp is 60～90 ℃.
12. in accordance with the method for claim 9, it is characterized in that, in step (1), roasting 4～8h between 400～650 ℃.
13. in accordance with the method for claim 9, it is characterized in that, front in step (1), by described inorganic materials roasting 4h at least between 400～650 ℃.
14. in accordance with the method for claim 9, it is characterized in that, in step (2), the sample that step (1) is obtained is crushed to median size≤100 μ m.
15. in accordance with the method for claim 9, it is characterized in that, in step (3), the sample dispersion that the mode that adopts high-speed stirring obtains step (2) is in the dispersion agent that contains the oil soluble radical initiator.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4298455A (en) * | 1979-12-31 | 1981-11-03 | Texaco Inc. | Viscosity reduction process |
| US4394250A (en) * | 1982-01-21 | 1983-07-19 | Chevron Research Company | Delayed coking process |
| US5006223A (en) * | 1989-09-29 | 1991-04-09 | Exxon Research And Engineering Company | Addition of radical initiators to resid conversion processes |
| CN1487056A (en) * | 2002-10-01 | 2004-04-07 | 曹炳铖 | Method of raising liquid yield during delayed coking |
| CN1560198A (en) * | 2004-03-04 | 2005-01-05 | 沈阳工业大学 | Additive for enhancing and delaying light oil recovery rate of coke apparatus |
| CN1928021A (en) * | 2006-09-06 | 2007-03-14 | 中国石油化工集团公司 | Auxiliary agent capable of improving delayed coking liquid yield, preparation method and application thereof |
| CN101215476A (en) * | 2007-12-28 | 2008-07-09 | 南京石油化工股份有限公司 | Assistant for catalytic cracking coking-inhibiting yield-increasing and preparing process thereof |
-
2010
- 2010-06-29 CN CN2010102115590A patent/CN102311756B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4298455A (en) * | 1979-12-31 | 1981-11-03 | Texaco Inc. | Viscosity reduction process |
| US4394250A (en) * | 1982-01-21 | 1983-07-19 | Chevron Research Company | Delayed coking process |
| US5006223A (en) * | 1989-09-29 | 1991-04-09 | Exxon Research And Engineering Company | Addition of radical initiators to resid conversion processes |
| CN1487056A (en) * | 2002-10-01 | 2004-04-07 | 曹炳铖 | Method of raising liquid yield during delayed coking |
| CN1560198A (en) * | 2004-03-04 | 2005-01-05 | 沈阳工业大学 | Additive for enhancing and delaying light oil recovery rate of coke apparatus |
| CN1928021A (en) * | 2006-09-06 | 2007-03-14 | 中国石油化工集团公司 | Auxiliary agent capable of improving delayed coking liquid yield, preparation method and application thereof |
| CN101215476A (en) * | 2007-12-28 | 2008-07-09 | 南京石油化工股份有限公司 | Assistant for catalytic cracking coking-inhibiting yield-increasing and preparing process thereof |
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