CN103525450A - Filling method of hydrocarbon oil catalytic cracking additive - Google Patents
Filling method of hydrocarbon oil catalytic cracking additive Download PDFInfo
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- CN103525450A CN103525450A CN201210241098.0A CN201210241098A CN103525450A CN 103525450 A CN103525450 A CN 103525450A CN 201210241098 A CN201210241098 A CN 201210241098A CN 103525450 A CN103525450 A CN 103525450A
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- catalytic cracking
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- oil catalytic
- charging method
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- 239000000654 additive Substances 0.000 title claims abstract description 79
- 230000000996 additive effect Effects 0.000 title claims abstract description 79
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 27
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 27
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 26
- 238000011049 filling Methods 0.000 title abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000003921 oil Substances 0.000 claims description 65
- 238000009834 vaporization Methods 0.000 claims description 13
- 230000008016 vaporization Effects 0.000 claims description 13
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 239000012190 activator Substances 0.000 claims description 3
- 239000003995 emulsifying agent Substances 0.000 claims description 3
- 239000012808 vapor phase Substances 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 230000002708 enhancing effect Effects 0.000 claims 1
- 235000003599 food sweetener Nutrition 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 239000003765 sweetening agent Substances 0.000 claims 1
- 239000000571 coke Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 2
- 239000007921 spray Substances 0.000 abstract 2
- 239000007789 gas Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000000889 atomisation Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000005336 cracking Methods 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000004533 oil dispersion Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- -1 hydrogen hydrocarbon Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002663 nebulization Methods 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 239000003027 oil sand Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a filling method of a hydrocarbon oil catalytic cracking additive, which is used for solving the problems that hydrocarbon oil yield is lowered, coke yield is increased, and the like as an existing catalytic cracking material cannot be completely atomized into tiny oil drops. According to the filling method, an additive and deionized water are mixed in a weight ratio of 1:25-1:500, preferably 1:100-1:200; the mixture is heated until being overheated and gasified, and mixed with atomized vapor in terms of 200mu g/g-5000mu g/g, preferably 800mu g/g-2000mu g/g in a spray nozzle mixing chamber so as to enter a lifting tube spray nozzle based on total weight of atomized vapor and the additive.
Description
Technical field
The present invention relates in the situation that not there is not hydrogen hydrocarbon oil catalytic cracking field, particularly a kind of hydrocarbon oil catalytic cracking additive charging method.
Background technology
As the main processing unit (plant) fluid catalytic cracking in oil refining field, mixing refining residual oil or entirely refining residual oil of vast scale is the powerful measure that improves ton crude oil processing profit.Constantly increasing the weight of of conventional catalytic cracking charging cut, make charging after nozzle, be difficult to all be atomized into small oil droplet, being present in the macromole hydrocarbon of low molecular hydrocarbon and low-pole in the outer solvated layer of the formed glue core of bituminous matter of large oil droplet is difficult to discharge completely, can not contact catalyst and participate in catalytic cracking reaction, this will cause the liquid yield of catalytic cracking unit to reduce, and coke yield increases.
The worker that refines oil both at home and abroad is for many years always in continuous effort, develop the surfactant additive of a large amount of different oil dispersion systems, as reinforcer, activator, emulsifying agent etc.), in order to improve the surface properties of hydrocarbon raw material, to improve the atomizing effect of hydrocarbon raw material.
In CN1429881A, mention a kind of method that catalytic cracking product distributes of improving, in stock oil, add 100 μ g/g reinforcers and 10 times of ratios to be rich in the hydrocarbon polymer auxiliary agent of aromatic hydrocarbons, on riser tube experimental installation, test, result shows that diesel yield increases by 1.76, light oil yield improves 1.54 percentage points, total liquid yield increases by 1.52 percentage points, and transformation efficiency improves 0.99 percentage point, and coking yield reduces 0.66 percentage point." petrochemical complex Journal of Chinese Universities " 2004,17 (2): 24～27, in one literary composition, the strengthening oil after long residuum and interpolation surface-active substance is fixed to a catalytic cracking reaction simultaneous test, in stock oil, add 200 μ g/g (m, to raw material) after reinforcer, transformation efficiency improves 4～6 percentage points, and yield of gasoline improves 2～5 percentage points, and dry gas yied increases nearly 2 percentage points, diesel yield declines 1～2%, coke yield 2 percentage points that decline.
Conventionally, additive is all directly to mix with stock oil, but practical application effect is undesirable, and additive amount is many.The reinforcer of trace joins in stock oil pipeline, and owing to can not full and uniformly mixing, dispersion effect is undesirable and can not get satisfied result of use.Catalytic cracking adopts Emulsified also to have problems, one, stock oil is before entering riser reactor nozzle, first to carry out the mixing and emulsifying of oil and water, need under low temperature, high speed conditions, be uniformly mixed, make it form emulsified feedstock, this not only will increase emulsifying device, and the emulsifying effectiveness of oil in water emulsion, stability, homogeneity is also difficult to guarantee; They are two years old, emulsification mixed solution has unavoidably the globule in flow process in device feeding line to be assembled, form not of uniform size, disperse the inhomogeneous globule, enter riser reactor instant vaporization, volume sharply expands thousand times, likely can cause system pressure fluctuation or affect catalyst fluidization state, making device fluctuation of service.
Summary of the invention
The present invention is directed to the deficiency of some additive dosing method, propose a kind of for hydrocarbon ils additive charging method, additive is carried out to atomization and disperse to be filled in reaction system, can make additive be dispersed in uniformly in stock oil with less molecule, improve the effect of additive.
A kind of hydrocarbon oil catalytic cracking additive charging method, it is characterized in that: additive and deionized water were by weight 1: 25～1: 100, within preferably 1: 50～1: 80, mix, mixture is heated to overheated vaporization, additive and atomizing steam are 200～5000 μ g/g by additive concentration in atomizing steam, after preferably 800～2000 μ g/g mix in steam mixer, enter into riser tube nozzle mixing section and mix with stock oil, in atomizing steam gross weight.
Described additive and deionized water mixture are heated to overheated vaporization, adopt steam generator or interchanger to carry out overheated gasification.
Described additive and deionized water mixture are heated to overheated vaporization, and after vaporization, vapor phase temperature is 140～350 ℃, preferably 250～330 ℃.
Described a kind of hydrocarbon oil catalytic cracking additive charging method, it is characterized in that: the concentration of additive increases gradually and reaches required balance concentration, first with 10 μ g/g additive capacity filling, stablize 1～2 hour, improving additive capacity to 20 μ g/g filling stablizes 1～2 hour again, with 30 μ g/g additive capacity filling, stablize 1～2 hour again, to being increased to gradually required balance filling concentration.
Described hydrocarbon oil catalytic cracking additive is the additive for catalytic cracking process, as reinforcer, activator, emulsifying agent, metal passivator, fall alkene auxiliary agent etc.
Described catalytic cracking charging comprises: the mixture of one or more of the extraction oil of crude oil, light ends oil, heavy distillate, vacuum residuum, long residuum, wax tailings, residual hydrogenation heavy oil, thermally splitting heavy oil, lube oil finishing, the tar of cracking of ethylene, refinery's sump oil, city sump oil, coal tar, shale oil, oil-sand heavy oil etc.
Compared with prior art, advantage of the present invention is:
Because hydrocarbon oil catalytic cracking additive of the present invention is to follow atomizing steam to enter together nozzle, additive first disperses through the water vapor of a large amount of atomizations, mix with stock oil again, can make like this additive better be dispersed in stock oil, the mixture flow that makes to form uniform oil bag vapour steam bubble, can make additive obtain maximum effect with minimum consumption; The minimizing additive amount of this using method maximizing, can not affect the quiet run of device, can not exert an influence to cracking product property; Additive is injected in riser tube nozzle together with atomizing steam mixture, at nozzle mixing section, useful effect due to atomization additive bioactive molecule, changed stock oil dispersion system character, oil, vapour interfacial state improve, and have promoted stock oil and atomizing steam to form the steam bubble mixture of uniform oil bag vapour.Mixture flow, from mixing section ejection, because system pressure discharges, and realizes efficient explosion atomization; This atomization dispersing method, more additive small molecules is fully contacted with stock oil, further strengthened riser tube feed nozzle function, improved the atomizing effect of stock oil, more tiny oil droplets grains are vaporized afterwards and catalyzer generation catalytic cracking reaction, liquefied gas and light oil yield are improved, and coke yield reduces, thereby obtains significant economic benefit.
Below in conjunction with accompanying drawing, embodiment, the present invention will be further described in detail, but do not limit use range of the present invention.
Embodiment
Fig. 1 is additive system block diagram of the present invention.First additive is injected in additive storage tank 11, after heating visbreaking, then through metering, flows automatically to additive thinning tank 12 in the ratio of the required injection additive of catalytically cracked stock; After the deionized water dilution that additive injects line metering injection through deionized water in additive thinning tank 12, containing the agent aqueous solution, from bottom by volume pump 13, enter interchanger or vapour generator 14; Contain the agent aqueous solution in interchanger or the interior vaporization of vapour generator 14 and reach after temperature of superheat, by entering steam mixer 15 containing vapor of additive arrival line 24; At steam mixer 15, include vapor of additive, mix with the atomizing steam entering by catalytic cracking nozzle atomization steam-in line 25, after mixing, atomizing steam enters nozzle line 26 by mixed aerosol steam, and the form that catalytic cracking atomizing steam enters nozzle is routinely mixed with stock oil.
On middle scale riser catalytic cracking experimental installation, choose a kind of additive, equilibrium catalyst and stock oil with Oil Refinery Industry production equipment, with identical test operation condition, carry out respectively two kinds of dosing method simultaneous tests of different additive concentration.Equilibrium catalyst used and stock oil physico-chemical property in Table 1, table 2, test conditions in Table 3, table 4.
Comparative example 1
By additive 50 μ g/g, in catalytically cracked stock gross weight, join in 90～110 ℃ of material tanks, after fully stirring, through the preheating of fuel oil preheating stove, make to reach preheating temperature again, enter subsequently riser tube and carry out cracking reaction.Table 4 testing data shows, uses after additive, and feed stock conversion improves 1.53 percentage points, yield of liquefied gas improves 0.11 percentage point, and light oil yield improves 1.38 percentage points, and total liquid is received and improved 1.55 percentage points, coke yield reduces by 0.40 percentage point, and dry gas yied is constant.
Comparative example 2
Identical with comparative example 1, additive capacity is 70 μ g/g, testing data is listed in table 4, feed stock conversion improves 1.93 percentage points, yield of liquefied gas improves 0.29 percentage point, and light oil yield improves 1.81 percentage points, and total liquid is received and improved 2.10 percentage points, coke yield reduces by 0.52 percentage point, and dry gas yied is constant.
Embodiment 1
Identical with contrast enforcement 1, different is that additive deionized water is mixed, and through vapour generator, it is reached after atomizing raw materials vapor temperature, enters riser tube nozzle mixing section and mixes with stock oil, and mixture carries out cracking reaction through nozzle ejection.Table 4 has been listed testing data, adopts the present invention, and feed stock conversion improves 3.58 percentage points, yield of liquefied gas improves 0.84 percentage point, and light oil yield improves 3.50 percentage points, and total liquid is received and improved 4.34 percentage points, coke yield reduces by 1.04 percentage points, and dry gas yied changes little.
Embodiment 2
Identical with embodiment 1, different is that additive capacity is adjusted to 70 μ g/g, it the results are shown in table 4, change after additive capacity, feed stock conversion improves 3.97 percentage points, and yield of liquefied gas improves 1.17 percentage points, light oil yield improves 4.11 percentage points, total liquid is received and is improved 5.28 percentage points, and coke yield reduces by 1.18 percentage points, and dry gas yied improves 0.12 percentage point.
Test-results shows, adds in different ways its effect of injecting additive also different.Adopt dosing method of the present invention can make additive be fully used, greatly improve the surface properties of stock oil, improved the nebulization efficiency of stock oil, directly sneak into dosing method in stock oil with additive and compare, while adding the additive of 50 μ g/g, feed stock conversion improves 2.05 percentage points, yield of liquefied gas improves 0.67 percentage point, light oil yield improves 2.12 percentage points, and total liquid is received and improved 2.79 percentage points, and coke yield reduces by 0.64 percentage point; While adding the additive of 70 μ g/g, feed stock conversion improves 2.14 percentage points, and yield of liquefied gas improves 0.88 percentage point, light oil yield improves 2.40 percentage points, total liquid is received and is improved 3.28 percentage points, and coke yield reduces by 0.66 percentage point, and dry gas yied increases by 0.11 percentage point; So, use dosing method of the present invention can obtain larger economic benefit.
Specific embodiment described in the present invention only, for the present invention is described, does not limit the scope of the invention.
Table 1 equilibrium catalyst main physical and chemical table 2 stock oil character
Table 3 test conditions
Table 4 product yield
Claims (9)
1. a hydrocarbon oil catalytic cracking additive charging method, it is characterized in that: additive and deionized water were by weight 1: 25～1: 100, within preferably 1: 50～1: 80, mix, mixture is heated to overheated vaporization, additive is after 200～5000 μ g/g mix in steam mixer with atomizing steam by additive concentration in atomizing steam, enter into riser tube nozzle mixing section and mix with stock oil, in atomizing steam gross weight.
2. according to a kind of hydrocarbon oil catalytic cracking additive charging method claimed in claim 1, it is characterized in that: additive with deionized water by weight mixing for 1: 50～1: 80, and mixture is heated to overheated vaporization.
3. according to a kind of hydrocarbon oil catalytic cracking additive charging method claimed in claim 1, it is characterized in that: additive is after 800～2000 μ g/g mix in steam mixer with atomizing steam by additive concentration in atomizing steam, enter into riser tube nozzle mixing section and mix with stock oil, in atomizing steam gross weight.
4. according to a kind of hydrocarbon oil catalytic cracking additive charging method claimed in claim 1, it is characterized in that: described additive and deionized water mixture are carried out overheated vaporization by steam generator or interchanger.
5. according to a kind of hydrocarbon oil catalytic cracking additive charging method claimed in claim 1, it is characterized in that: described additive and deionized water mixture are heated to overheated vaporization, after vaporization, vapor phase temperature is 140～350 ℃.
6. according to a kind of hydrocarbon oil catalytic cracking additive charging method claimed in claim 1, it is characterized in that: described additive and deionized water mixture are heated to overheated vaporization, after vaporization, vapor phase temperature is 250～330 ℃.
7. according to a kind of hydrocarbon oil catalytic cracking additive charging method claimed in claim 1, it is characterized in that: described additive concentration increases gradually and reaches required balance concentration.
8. according to a kind of hydrocarbon oil catalytic cracking additive charging method claimed in claim 1, it is characterized in that: described hydrocarbon oil catalytic cracking additive is at least one additive for catalytic cracking process.
9. according to a kind of hydrocarbon oil catalytic cracking additive charging method claimed in claim 1, it is characterized in that: described hydrocarbon oil catalytic cracking additive is reinforcer, activator, emulsifying agent, metal passivator, fall at least one in alkene auxiliary agent, sweetening agent, propylene enhancing auxiliary agent.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210241098.0A CN103525450A (en) | 2012-07-05 | 2012-07-05 | Filling method of hydrocarbon oil catalytic cracking additive |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210241098.0A CN103525450A (en) | 2012-07-05 | 2012-07-05 | Filling method of hydrocarbon oil catalytic cracking additive |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114350401A (en) * | 2021-12-30 | 2022-04-15 | 金澳科技（湖北）化工有限公司 | Method for reducing raw oil viscosity and improving yield |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1258713A (en) * | 1998-12-29 | 2000-07-05 | 中国石油化工集团公司 | Sulfur transferring assistant for catalytic cracking of hydrocarbon and its usage |
| CN101497810A (en) * | 2009-02-24 | 2009-08-05 | 沧州鑫泰精细化工厂 | Catalytic cracking multifunctional strengthened additive |
-
2012
- 2012-07-05 CN CN201210241098.0A patent/CN103525450A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1258713A (en) * | 1998-12-29 | 2000-07-05 | 中国石油化工集团公司 | Sulfur transferring assistant for catalytic cracking of hydrocarbon and its usage |
| CN101497810A (en) * | 2009-02-24 | 2009-08-05 | 沧州鑫泰精细化工厂 | Catalytic cracking multifunctional strengthened additive |
Non-Patent Citations (2)
| Title |
|---|
| 刘淑芳等: ""改善催化裂化产品分布的添加剂及其应用研究"", 《河南化工》 * |
| 孙昱东等: ""乳化重油高温稳定性及催化裂化反应性能研究"", 《石油大学学报（自然科学版）》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114350401A (en) * | 2021-12-30 | 2022-04-15 | 金澳科技（湖北）化工有限公司 | Method for reducing raw oil viscosity and improving yield |
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Application publication date: 20140122 |