CN105586068B - A kind of processing method of contact agent and heavy petroleum hydrocarbon - Google Patents
A kind of processing method of contact agent and heavy petroleum hydrocarbon Download PDFInfo
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Abstract
A kind of method for processing heavy petroleum hydrocarbon the present invention relates to contact agent and using the contact agent, the contact agent are made of aluminium oxide and magnesia.The contact cracking reaction that the contact agent has high thermal conductivity, can realize high reaction temperature, short residence time during fluid bed or riser process heavy petroleum hydrocarbon, so as to effectively improve liquid yield and reduce dry gas and coke yield.
Description
Technical field
A kind of processing method of heavy petroleum hydrocarbon the present invention relates to contact agent and using the contact agent.
Background technology
With the rapid development of global economy, the demand of the energy is increasingly increased, and petroleum resources are short, international oil price
It is high, petroleum resources are inferior, increasingly strict for oil Refining Technologies, more stringent requirements are proposed for heaviness and environmental requirement：Heavy
The efficient green conversion of oil.On the one hand it requires " to eat dry squeeze only " as far as possible to feedstock oil, on the other hand seek to energy saving.
Currently, including the catalytic cracking of heavy oil, fluidisation with the technique of fluid bed or riser processing heavy, inferior feedstock oil
Coking, flexicoking etc. are paid more and more attention.When such technique processing heavy oil, fluidizing agent serves not only as catalytic center, together
The carrier of Shi Zuowei heats and coke.
Thermocracking process with the characteristics of high reaction temperature, short residence time is in many necks such as heavy oil modification, catalytic cracking
There is application in domain.When using fluid bed or riser as reactor processing heavy oil feedstock oil, feedstock oil is sprayed by nozzle at high speeds
Enter, fast reaction after being contacted with thermo-contact agent, light petroleum gas and the contact agent quick separating of generation, and carries charcoal contact agent and enter again
Raw unit is regenerated, this process inhibits crackate that two occur under the high temperature conditions by pyrolytic cracking and short residence time
Secondary cracking reaction, to obtain maximum liquid yield and smaller coke and dry gas yied.Such technique is carried out both at home and abroad
A large amount of research, develops various short residence time process, such as the rapid cleavage technique that this company of stone weber develops,
Patent, which is shown, to select thermophore according to raw material and target product；The HLT techniques of Ivanhoe Energy Inc. exploitations；Road reaches
The fluid catalytic cracking technology that you propose, the process reactor belong to fluidized bed at elevated reactor, and patentability is special reaction
Cell structure is conducive to raw material and regenerative agent, and mixing reaches high reaction temperature rapidly.Contact agent in such technology contains with catalysis
Active catalyst, inert quartz sand, coke, low specific surface area calcined kaolin etc..These technologies are all with corresponding
Patent equipment reaches high reaction temperature and short residence time, the thermal conductivity of catalyst carrier or catalyst itself to reaction process
Matter is simultaneously not concerned with.
Invention content
It is connect the purpose of the present invention is to provide a kind of new contact agent that can greatly improve liquid yield and using this
The processing method for touching the heavy petroleum hydrocarbon of agent.
Aluminium oxide high mechanical strength, thermal stability and good heat-transfer, the carrier as catalysis material are drawn extensively
With.It was found by the inventors of the present invention that using the material for containing aluminium oxide and magnesia as contact agent, existing fluid bed is used
Or riser reactor can be obtained high liquid yield and lower dry gas, coke yield as contact cracker, from
And substantially reduce the requirement to equipment.
According to an aspect of the present invention, the present invention provides a kind of contact agent, and the contact agent is by aluminium oxide and magnesia.
According to another aspect of the present invention, the present invention provides a kind of processing method of heavy petroleum hydrocarbon, this method includes
In the case where facing hydrogen or conditions of non-hydrogen, heavy petroleum hydrocarbon and contact agent are being contacted into transmission of heat by contact in cracker, making heavy stone
Petroleum hydrocarbon is in contact cracking reaction, which is characterized in that the contact agent is above-mentioned contact agent provided by the invention.
Contact agent provided by the invention can quick transferring heat energy, can be realizing high reaction temperature, short residence time
The heat cracking reaction being characterized, for complicated as technology without being carried out to equipment when processing heavy, inferior raw material
Improvement can produce more light-end products and minimum coke and dry gas.For example, from following embodiments 1 as can be seen that using this
The contact agent that invention provides carries out contact cracking to inferior heavy oil, can be obtained up in conventional heavy oil is fixed fluidized bed
81.01% liquid yield, and the dry gas down to 1.77% and 17.01%, coke yield.It traces it to its cause, it may be possible to because：
(1) contact agent has the function of quick conductive as heat carrier, makes thermal cracking lighter products fast transfer to gas phase,
The generation for preventing secondary cracking from reacting reduces the yield of coke and dry gas；
(2) contact agent itself prevents residual oil overcracking without catalytic cracking activity；
(3) contact agent has larger duct, is more suitable for the transfer of slag oil cracking product char.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
According to an aspect of the present invention, the present invention provides a kind of contact agent, and the contact agent is by aluminium oxide and magnesia group
At.
Under preferable case, on the basis of the total amount of the contact agent, the content of aluminium oxide is 20-80 weight %, magnesia
Content be 20-80 weight %.
Under preferable case, specific surface area >=10m of the contact agent2/ g, Kong Rongwei 0.05-0.5cm3/g.Further preferred feelings
Under condition, the specific surface area of the contact agent is 50-150m2/ g, Kong Rongwei 0.05-0.4cm3/g.It can be by selecting suitable oxidation
Aluminium and magnesia and ratio between the two is suitably adjusted to obtain above structure parameter.In above-mentioned preferred specific surface area
Under the conditions of Kong Rong, the quality of liquid oil can be further increased.
Due to existing magnesia or to be powdered, or the graininess for grain size at 200 μm or more, in order to obtain grain
The magnesium oxide particle of diameter within the above range, the present invention is by the way that existing magnesium oxide particle or powder to be beaten together with magnesium chloride
After carry out mist projection granulating, then roast.The weight ratio of magnesium oxide particle or powder and magnesium chloride is preferably 1000：10-200, it is excellent
Select 1000：The weight ratio of 50-100, magnesium oxide particle or powder and magnesium chloride is preferably 1000：500-1000.The temperature of roasting
It can be 400-800 DEG C, preferably 500-700 DEG C, the time of roasting can be 2-8 hours, preferably 4-6 hours.Mist projection granulating
Concrete operations and condition it is known to those skilled in the art, details are not described herein.
In the case of further preferably, in order to obtain higher liquid yield, the magnesia is foramen magnum-mesoporous magnesia, greatly
The aperture in hole is 50-100nm, and mesoporous aperture is 15-50nm.Wherein macropore accounts for 20-50 volumes %, mesoporous to account for 30-50 bodies
Product %.
Similarly, since existing aluminium oxide is either powdered or for grain size at 200 μm or more graininess, in order to obtain
The alumina particle of grain size within the above range, the present invention by by existing alumina particle or powder together with Aluminum sol
Mist projection granulating is carried out after mashing, is then roasted.The weight ratio of alumina particle or powder and Aluminum sol is preferably 1-10：1, preferably
3-8：1, alumina particle or the weight ratio of powder and the water of mashing are preferably 2-5：1.The temperature of roasting can be 400-800
DEG C, preferably 500-700 DEG C, the time of roasting can be 2-8 hours, preferably 4-6 hours.The concrete operations of mist projection granulating and item
Part is known to those skilled in the art, and details are not described herein.
In the present invention, the aluminium oxide in the contact agent can be any type presoma such as amorphous hydroted alumina, intend
Boehmite, boehmite etc. are prepared by spray roasting mode, and the aluminium oxide can be α-Al2O3、γ-
Al2O3、θ-Al2O3In it is one or more.
In order to obtain better fluidizing performance and abrasion resistance properties, the preferably described contact agent shape is microballoon shape, into one
The average grain diameter of the step preferably contact agent is 50-75 μm, and the particle size range of the still more preferably described contact agent is 20-200 μ
m。
The thermal coefficient of aluminium oxide at 25~34W/ (mK), the thermal coefficient of magnesia at 25~37W/ (mK), because
In this present invention, the thermal coefficient of the contact agent is 25-40W/ (mK), preferably 25-35W/ (mK).In above-mentioned preferred model
In enclosing, contact agent itself has good heat conductivility, thus in the contact agent and heavy oil petroleum hydrocarbon in fluid bed or promotion
When being contacted in pipe reactor, contact agent can give self-contained heat transfer to contact agent surface oil reservoir more quickly, and make
In higher temperature thermal cracking, thermal cracking lighter products fast transfer to gas phase, the hair for preventing secondary cracking from reacting occur for oil reservoir
It is raw, to reduce the yield of coke and dry gas.
In the present invention, unless otherwise indicated, specific surface area and Kong Rong are automatically compared using Quantachrome companies AS-6
Surface area and lacunarity analysis instrument are measured by static state low temperature capacity sorbent method, are obtained according to BET equation calculations；Thermal coefficient makes
Thermal constant analyzer is produced with Hot Disk AB companies of Sweden, is measured using moment state mode.
Contact agent provided by the invention has preferable abrasion resistance and higher thermal coefficient, in contact cracking process
Middle heat carrier and coke carrier and fluidizing reagent as cracking process, can be within the shortest time by the heat entrained by contact agent
Amount is transmitted to surface oil reservoir, to realize high reaction temperature and short contacting time.Contact agent provided by the invention especially suitable for
It is processed in heavy petroleum hydrocarbon method as the fluid bed of main feature or riser using high reaction temperature and short contacting time.
The preparation method of contact agent provided by the invention is simple, can be by straight by grain size aluminium oxide appropriate and magnesia
The tool that picks is mixed to get.
According to another aspect of the present invention, the present invention also provides a kind of processing method of heavy petroleum hydrocarbon, this method packets
It includes in the case where facing hydrogen or conditions of non-hydrogen, by heavy petroleum hydrocarbon and contact agent transmission of heat by contact, heavy petroleum hydrocarbon is made to be in contact cracking
Reaction, which is characterized in that the contact agent is the above-mentioned contact agent provided of the present invention.
According to the present invention, under conditions of non-hydrogen, the condition for contacting cracking reaction preferably includes：Reaction temperature 450-650
DEG C, weight (hourly) space velocity (WHSV) 1-100h-1, the mass ratio of contact agent and heavy oil feedstock is 1-30：1, it contacts gas phase in cracker and stops
The mass ratio of time 0.5-2.0s, vapor and heavy oil feedstock is 0.05-1：1.
Under hydro condition, the condition for contacting cracking reaction preferably includes：450-650 DEG C of reaction temperature, weight (hourly) space velocity (WHSV) 1-
100h-1, the mass ratio of contact agent and heavy oil feedstock is 1-30：1, the mass ratio of vapor and heavy oil feedstock is 0.05-1：1, always
Pressure is 0-1MPa, hydrogen partial pressure 0.1-0.5MPa, hydrogen-oil ratio 10-1500m3/m3, contact gas phase in cracker and stop
Time 0.5-4.0s.In the present invention, unless stated otherwise, pressure is gauge pressure.
The heating rate that wherein heavy petroleum hydrocarbon is heated to reaction temperature is preferably 20-500 DEG C/s.
According to the preferred embodiment of the present invention, the processing method further include will generate can distillate out of reactor
Rapid cooling after distillating, deposition has the contact agent to be generated of coke to enter gasification unit.Under preferable case, generation can distillate it is excellent
Choosing is cooled to 350 DEG C or less after being distillated out of reactor in 0.5s.Thus secondary cracking and the condensation reaction of oil gas are avoided,
Reduce device fouling, while product characteristics being made to stablize.
In gasification unit, contact cracking reaction gained contact agent to be generated enters in fluidized-bed gasifier, is containing oxygen
In the presence of gasifying agent, make the charcoal on contact agent and gasifying agent reaction, obtains regeneration contact agent and be rich in CO, H2Gasification gas.Stream
Change reaction condition in bed gasifier to preferably include：Gas residence time is 0.5-60 seconds, preferably 1.0-10 seconds.The gas of dense bed
It is 550-1000 DEG C, preferably 600-950 DEG C to change temperature；The linear velocity 0.05-0.6m/s of dense bed, preferably 0.2-0.6m/
s.Compared with prior art, gasification temperature is greatly reduced, while the structure and property of contact agent will not be destroyed.
It is preferred that oxygen mole fraction is 5%-30% in gasifying agent, remaining for nitrogen or vapor or carbon dioxide or it
In two or more mixture.Oxygen mole fraction is 5%-20% in further preferred gasifying agent.
Wherein, the sulphur in gasification gas is mainly with H2The form of S and COS exists.Gasification reaction institute occurs for coke on spent agent
H in the gasification gas of generation2S and COS is accounted in gasification gas more than 99.0% (volume) of total sulfur, to be easily recycled sulphur, entirely
Technical process environmental protection.
Further preferably in the case of, processing method of the invention further include will gasify pneumatic transmission enter sulfur recovery unit remove sulphur,
And by the gasification gas after desulfurization after Water gas shift/WGS device carries out Water gas shift/WGS, isolated hydrogen and CO2Or it will take off
Gasification gas after sulphur as fuel gas application, or for generate electricity or as boiler oil occur steam.
Removing to the sulfur-containing compound in gasification gas is that gasification gas enters a COS removing means, the COS first
Removing means can convert COS to H2The further Recovered sulphur of S can also absorb COS and recycle COS.COS removing means institute
The method of use can be organic amine absorption process, hydroconversion process, hydrolysis method, oxidation conversion method, absorption method etc..These sides
Method can convert COS to H2S.It can also use porous solid material CO absorption S that it be made to be enriched in the surface of solids, go forward side by side one
Step obtains COS.From H2The method of S Recovered sulphur refers to industrial common method, such as claus process.
Compared with prior art, the beneficial effects are mainly as follows the following aspects：
First, contact agent thermal coefficient of the invention is high, therefore can be easily achieved being brought rapidly up for feedstock oil, makes liter
Warm rate reduces liquid phase reactor up to 20~500 DEG C/s, reduces secondary response, reduces coke and dry gas yied, selectivity
Be stripped of intrinsic coke precursor.
Secondly, the hole of the contact agent is bigger, reduces and generates massive particles in cracker, keeps fluidisation smooth,
Reduce the various inner members in cracker, reduces dry gas and coke yield.
In addition, the preferred embodiment of method provided by the present invention is integrated with heavy oil deep processing and superfluous carbonaceous residue
Coke more than needed is gasified while producing light oil using two aspects in gasifier rationally, (CO+ is rich in gained gasification gas
H2), this partial gasification gas can be used as fuel gas, can also be used to transformation and hydrogen production, can also be used to the steaming that generates electricity or generate
Vapour.Rear CO is used in these processes2100% is basically reached, can trap, reduce refinery's carbon emission.
According to the present invention, the heavy petroleum hydrocarbon can be that existing various density are big, carbon residue is high, metal and sulfur content
High inferior oil material, for example, the carbon residue of the heavy petroleum hydrocarbon can be 10-45 weight %, tenor can be 25-
1000μg/g.Specifically, the heavy petroleum hydrocarbon can be reduced crude, decompression residuum, visbroken resids, be hydrocracked tail
It is one or more in oil, deasphalted oil.
The content for further illustrating the present invention, but being not intended to limit the present invention below by embodiment.
Embodiment 1-4 and comparative example 1-3 are used to prepare contact agent.
Comparative example 1
3000g macropores boehmite (Shandong Aluminum Plant's offer) is stirred evenly with 800g deionized waters, under stiring after
It is continuous that 600g Aluminum sols (Qilu Petrochemical Company's catalyst plant production, alumina content are 22.5 weight %) are added, 20min is stirred,
Slurries are spray-dried on spray-drying installation, is then roasted 5 hours at 600 DEG C, obtains contact agent, number D1, grain size
For range at 20 μm -200 μm, composition and physical property are shown in Table 1.
Comparative example 2
By 1000g macropores magnesia, (thickness Dehua, Shandong Weifang work, for particle size range at 20 μm -200 μm, average grain diameter is 38 μ
M) it is stirred evenly with 800g deionized waters, continuously adds 80g magnesium chlorides under stiring, stirred 40min, slurries are being spray-dried
Be spray-dried on device, then roasted 5 hours at 600 DEG C, obtain contact agent, number D2, particle size range at 20 μm -200 μm,
Aperture accounts for 25 volume % more than 50nm, and the mesoporous of aperture 20nm accounts for 43 volume %.Composition and physical property are shown in Table 1.
Embodiment 1
Contact agent in comparative example 1 and comparative example 2 is pressed into D1：D2 is 8：2 weight ratio uses the mode of mechanical mixture
It is uniformly mixed, obtains contact agent, number A1, composition and physical property are shown in Table 1.
Embodiment 2
Contact agent in comparative example 1 and comparative example 2 is pressed into D1：D2 is 2：8 ratio is mixed using the mode of mechanical mixture
Uniformly, contact agent, number A2 are obtained, composition and physical property are shown in Table 1.
Embodiment 3
By 3000g macropores boehmite, (Shandong Aluminum Plant provides, and for particle size range at 20 μm -200 μm, average grain diameter is 43 μ
M) stirred evenly with 800g deionized waters, continuously add under stiring 500g Aluminum sols (production of Qilu Petrochemical Company catalyst plant,
Alumina content is 25 weight %), 20min is stirred, slurries are spray-dried on spray-drying installation, is then roasted at 1000 DEG C
It burns 5 hours, obtains alumina particle, for particle size range at 20 μm -200 μm, average grain diameter is 65 μm, and thermal coefficient is 33W/ (m
K)。
By 1000g macropores magnesia, (thickness Dehua, Shandong Weifang work, for particle size range at 20 μm -200 μm, average grain diameter is 38 μ
M) it is stirred evenly with 800g deionized waters, continuously adds 180g magnesium chlorides under stiring, stir 40min, slurries are dry in spraying
It is spray-dried on dry device, is then roasted 5 hours at 800 DEG C, obtain magnesium oxide particle, particle size range is at 20 μm -200 μm, hole
Macropore of the diameter more than 50nm accounts for 35 volume %, and aperture is that the mesoporous of 20nm accounts for 37 volume %.
By above-mentioned aluminium oxide and magnesia by weight 1：1 mechanical mixture is uniform, obtains contact agent, number A3, grain size
For range at 20 μm -200 μm, composition and physical property are shown in Table 1.
Embodiment 4
Contact agent is prepared in the way of embodiment 3, unlike, foramen magnum-mesoporous magnesia is replaced by microporous alumina magnesium,
Contact agent is obtained, number A4, for particle size range at 20 μm -200 μm, composition and physical property are shown in Table 1.
Comparative example 3
Kaolin (Suzhou carclazyte) and boehmite (Shandong Aluminum Plant's production) is levigate, and average grain diameter is 1.0 μm.It takes
12kg deionized waters are added in 6kg kaolin, stir 30 minutes.1.5kg boehmites are taken, 2.25kg deionized waters are added, stir
It mixes uniformly, nitric acid is added and adjusts pH value to 1.5.Two kinds of slurries are mixed 30 minutes, spray shaping roasts at 600 DEG C
Sample is obtained within 60 minutes, number D3, for grain particle size range at 20 μm -200 μm, composition and physical property are shown in Table 1.
Table 1
| Contact agent sample number into spectrum | A1 | A2 | A3 | A4 | D1 | D2 | D3 |
| Aluminium oxide, % | 80 | 20 | 50 | 50 | 100 | 0 | 51.5 |
| Magnesia, % | 20 | 80 | 50 | 50 | 0 | 100 | 0 |
| Silica, % | 0 | 0 | 0 | 0 | 0 | 0 | 45.4 |
| Thermal coefficient (W/mK) | 31 | 27 | 30 | 30 | 33 | 25 | 20 |
| Specific surface area (m2/g) | 116 | 107 | 68 | 187 | 119 | 104 | 37 |
| Pore volume (mL/g) | 0.40 | 0.37 | 0.16 | 0.48 | 0.41 | 0.36 | 0.10 |
| Average grain diameter (μm) | 66 | 65 | 66 | 65 | 67 | 65 | 66 |
Embodiment 5-8 and comparative example 4-6
Using the fixed fluidized bed experimental provision progress heavy petroleum hydrocarbon of heavy oil, remaining property is shown in Table 2) contact cracking experiments.It urges
Agent reserve is 300 grams, 500 DEG C of reaction temperature, weight (hourly) space velocity (WHSV) 5h-1, agent oil quality is than 7, and gas phase is stopped in contact cracker
Stay time 1s, the mass ratio of vapor and heavy oil feedstock is 0.5：1, crackate distribution experiments result is shown in table 3.
Table 2
| Project | Data | Project | Data |
| Density (20 DEG C)/(gcm-3) | 1.0021 | Ca | 1.0 |
| W (carbon residue)/% | 18.9 | Cu | <0.1 |
| Average molecular mass (VPO) | 567 | Four components/% | |
| Element composition/% | Saturation point | 30.1 | |
| C | 86.43 | Fragrance point | 34.5 |
| H | 10.54 | Colloid | 17.4 |
| S | 2.60 | Asphalitine | 18.0 |
| N | 0.36 | Gas-chromatography boiling range/DEG C | |
| n(H)/n(C) | 1.46 | Initial boiling point | 170 |
| Tenor/(μ gg-1) | 5% | 300 | |
| Ni | 46.0 | 10% | 353 |
| V | 299.0 | 30% | 482 |
| Fe | 18.2 | 50% | 605 |
| Na | 3.0 | 70% | 706 |
Table 3
From table 3 it can be seen that contact agent provided by the invention receives (liquefaction than contrast medium D3 liquid under identical reaction conditions
Gas, gasoline, diesel oil and heavy oil fraction) nearly 12 percentage points are improved, coke yield has dropped about 10 percentage points.
Embodiment 9
By contact agent and carbon residue that number is A1 be 15.10 weight %, metal is 50 μ g/g, sulfur content 1.12%
The petroleum hydrocarbon heavy oil of (quality) is in contact cracking reaction in contact Cracking Unit reactor, contacts the technique item of cracking reaction
Part is：460 DEG C of cracking temperature, weight (hourly) space velocity (WHSV) 10h-1, agent oil quality is than 10, and for water oil quality than 0.1, feedstock oil is heated to reaction
The heating rate of temperature is 150 DEG C/s, and the gas phase residence time is 0.8s.Generate can distillate distillated out of reactor after
350 DEG C or less are cooled in 0.5s.The coke content of gained spent agent contact agent containing charcoal (spent agent) is 1.4 weight %.
Dry gas yied is 1.1% in gained crackate, coke yield 13.60%, and it is 84.91% that liquid, which is received,.Green coke because
Sub- coke/carbon residue is 0.9.
Spent agent enters gasifier after stripping.Gas linear velocity is 0.25m/s in dense bed, and 620 DEG C of temperature is passed through
The gas of oxygen-containing 12.3% (mole), vapor 87.7% (mole), gas residence time 1.5 seconds.(CO+H in gasification gas2)/
CO2Molar ratio be 1.23, gasify gas in (butt) (CO+H2) molar content reach nearly 54.5%, H2S accounts for total sulfur in gasification gas
95.3% (volume), COS account for gasification gas in total sulfur 4.5% (volume).Contact agent after regeneration returns in cracker.
Embodiment 10
By contact agent and carbon residue that number is A2 be 18.10 weight %, metal is 200 μ g/g, sulfur content 1.12%
The petroleum hydrocarbon heavy oil of (quality) is in contact cracking reaction in contact Cracking Unit reactor, contacts the technique item of cracking reaction
Part is：500 DEG C of cracking temperature, weight (hourly) space velocity (WHSV) 20h-1, agent oil quality is than 7, and for water oil quality than 0.2, feedstock oil is heated to reaction
The heating rate of temperature is 100 DEG C/s, and the gas phase residence time is 1.0s.Generate can distillate distillated out of reactor after
350 DEG C or less are cooled in 0.5s.The coke content of gained spent agent contact agent containing charcoal (spent agent) is 2.4 weight %.
Dry gas yied is 1.8% in gained crackate, coke yield 16.83%, and it is 81.37% that liquid, which is received,.Green coke because
Sub- coke/carbon residue is 0.93.
Spent agent enters gasifier after stripping.Gas linear velocity is 0.12m/s in dense bed, and 680 DEG C of temperature is passed through
Air, gas residence time 5 seconds.(CO+H in gasification gas2)/CO2Molar ratio be 1.32, gasify gas in (butt) (CO+H2)
Molar content reaches nearly 56.1%, H2S accounts for 93.4% (volume) of total sulfur in gasification gas, and COS accounts for 4.3% of total sulfur in gasification gas
(volume).Contact agent after regeneration returns in cracker.
Embodiment 11
By contact agent and carbon residue that number is A3 be 35.0 weight %, metal is 425 μ g/g, sulfur content 3.12%
The petroleum hydrocarbon heavy oil of (quality) is in contact cracking reaction in contact Cracking Unit reactor, contacts the technique item of cracking reaction
Part is：520 DEG C of cracking temperature, weight (hourly) space velocity (WHSV) 50h-1, agent oil quality is than 20, and for water oil quality than 0.5, feedstock oil is heated to reaction
The heating rate of temperature is 200 DEG C/s, and the gas phase residence time is 0.5s.Generate can distillate distillated out of reactor after
350 DEG C or less are cooled in 0.5s.The coke content of gained spent agent contact agent containing charcoal (spent agent) is 1.6 weight %.
Dry gas yied is 1.2% in gained crackate, coke yield 31.85%, and it is 66.95% that liquid, which is received,.Green coke because
Sub- coke/carbon residue is 0.91.
Spent agent enters gasifier after stripping.Gas linear velocity is 0.40m/s in dense bed, and 560 DEG C of temperature is passed through
The gas of oxygen-containing 30% (mole), vapor 40% (mole), carbon dioxide 30% (mole), gas residence time 50 seconds.Gas
Change (CO+H in gas2)/CO2Molar ratio be 1.4, gasify gas in (butt) (CO+H2) molar content reach nearly 56.0%, H2S is accounted for
96.1% (volume) of total sulfur in gasification gas, COS account for 3.8% (volume) of total sulfur in gasification gas.Contact agent after regeneration returns
In cracker.
Embodiment 12
By contact agent and carbon residue that number is A1 be 15.10 weight %, metal is 50 μ g/g, sulfur content 1.12%
The petroleum hydrocarbon heavy oil of (quality) is in contact cracking reaction in contact Cracking Unit reactor, contacts the technique item of cracking reaction
Part is：468 DEG C of cracking temperature, weight (hourly) space velocity (WHSV) 9h-1, agent oil quality is than 12, and for water oil quality than 0.15, feedstock oil is heated to reaction
The heating rate of temperature is 120 DEG C/s, and the gas phase residence time is 0.75s, and gross pressure (gauge pressure) is 0.5MPa, and hydrogen partial pressure is
0.1MPa, hydrogen-oil ratio 1000m3/m3.Generate can distillate distillated out of reactor after be cooled in 0.5s 350 DEG C with
Under.The coke content of gained spent agent contact agent containing charcoal (spent agent) is 1.2 weight %.
Dry gas yied is 1.12% in gained crackate, coke yield 13.89%, and it is 84.99% that liquid, which is received,.
Green coke factor coke/carbon residue is 0.92.
Spent agent enters gasifier after stripping.Gas linear velocity is 0.25m/s in dense bed, and 620 DEG C of temperature is passed through
The gas of oxygen-containing 12.3% (mole), vapor 87.7% (mole), gas residence time 1.5 seconds.(CO+H in gasification gas2)/
CO2Molar ratio be 1.32, H2S accounts for 95.7% (volume) of total sulfur in gasification gas, and COS accounts for 3.8% (body of total sulfur in gasification gas
Product).Contact agent after regeneration returns in cracker.
Embodiment 13
By contact agent and carbon residue that number is A2 be 18.10 weight %, metal is 250 μ g/g, sulfur content 1.52%
The petroleum hydrocarbon heavy oil of (quality) is in contact cracking reaction in contact Cracking Unit reactor, contacts the technique item of cracking reaction
Part is：488 DEG C of cracking temperature, weight (hourly) space velocity (WHSV) 18h-1, agent oil quality is than 10, and than 0.35, feedstock oil is heated to anti-water oil quality
It is 120 DEG C/s to answer the heating rate of temperature, and the gas phase residence time is 1.75s, and gross pressure (gauge pressure) is 0.8MPa, and hydrogen partial pressure is
0.3MPa, hydrogen-oil ratio 200m3/m3.Generate can distillate distillated out of reactor after be cooled in 0.5s 350 DEG C with
Under.The coke content of gained spent agent contact agent containing charcoal (spent agent) is 1.7 weight %.
Dry gas yied is 1.75% in gained crackate, coke yield 16.83%, and it is 81.42% that liquid, which is received,.
Green coke factor coke/carbon residue is 0.93.
Spent agent enters gasifier after stripping.Gas linear velocity is 0.20m/s in dense bed, and 680 DEG C of temperature is passed through
The gas of oxygen-containing 22.3% (mole), vapor 77.7% (mole), gas residence time 3 seconds.(CO+H in gasification gas2)/CO2
Molar ratio be 1.23, H2S accounts for 94.6% (volume) of total sulfur in gasification gas, and COS accounts for 3.9% (body of total sulfur in gasification gas
Product).Contact agent after regeneration returns in cracker.
Embodiment 14
By contact agent and carbon residue that number is A3 be 35.0 weight %, metal is 550 μ g/g, sulfur content 3.25%
The petroleum hydrocarbon heavy oil of (quality) is in contact cracking reaction in contact Cracking Unit reactor, contacts the technique item of cracking reaction
Part is：535 DEG C of cracking temperature, weight (hourly) space velocity (WHSV) 38h-1, agent oil quality is than 15, and than 0.45, feedstock oil is heated to anti-water oil quality
It is 120 DEG C/s to answer the heating rate of temperature, and the gas phase residence time is 1.75s, and gross pressure (gauge pressure) is 0.7MPa, and hydrogen partial pressure is
0.2MPa, hydrogen-oil ratio 400m3/m3.Generate can distillate distillated out of reactor after be cooled in 0.5s 350 DEG C with
Under.The coke content of gained spent agent contact agent containing charcoal (spent agent) is 5.3 weight %.
Dry gas yied is 1.21% in gained crackate, coke yield 31.85%, and it is 66.94% that liquid, which is received,.
Green coke factor coke/carbon residue is 0.91.
Spent agent enters gasifier after stripping.Gas linear velocity is 0.20m/s in dense bed, and 680 DEG C of temperature is passed through
The gas of oxygen-containing 22.3% (mole), vapor 77.7% (mole), gas residence time 3 seconds.(CO+H in gasification gas2)/CO2
Molar ratio be 1.45, H2S accounts for 95.0% (volume) of total sulfur in gasification gas, and COS accounts for 4.1% (body of total sulfur in gasification gas
Product).Contact agent after regeneration returns in cracker.
Comparative example 7
By activated carbon (identical as 3 source of embodiment) and carbon residue be 35.0 weight %, metal is 550 μ g/g, sulfur content
It is in contact cracking reaction in contact Cracking Unit reactor for the petroleum hydrocarbon heavy oil of 3.25% (quality), contacts cracking reaction
Process conditions be：535 DEG C of cracking temperature, weight (hourly) space velocity (WHSV) 38h-1, agent oil quality is than 15, and water oil quality is than 0.45, feedstock oil quilt
The heating rate for being heated to reaction temperature is 120 DEG C/s, and the gas phase residence time is 1.75s, and gross pressure (gauge pressure) is 0.7MPa, hydrogen
Partial pressure is 0.2MPa, hydrogen-oil ratio 400m3/m3.Generate can distillate distillated out of reactor after be cooled in 0.5s
350 DEG C or less.The coke content of gained spent agent contact agent containing charcoal (spent agent) is 2.8 weight %.
Dry gas yied is 2.1% in gained crackate, coke yield 42.0%, and it is 55.9% that liquid, which is received,.
Green coke factor coke/carbon residue is 1.2.
Spent agent enters gasifier after stripping.Gas linear velocity is 0.20m/s in dense bed, and 680 DEG C of temperature is passed through
The gas of oxygen-containing 22.3% (mole), vapor 77.7% (mole), gas residence time 3 seconds.(CO+H in gasification gas2)/CO2
Molar ratio be 1.35, H2S accounts for 94.7% (volume) of total sulfur in gasification gas, and COS accounts for 4.5% (body of total sulfur in gasification gas
Product).Contact agent after regeneration returns in cracker.
By embodiment 14 as can be seen that embodiment 14 is by taking contact agent provided by the present invention compared with comparative example 7
And application method, dry gas reduce 0.9 percentage point, coke reduces 10.2 percentage points, and liquid, which is received, improves 11.0 percentage points, simultaneously
(butt) (CO+H in gasification gas2) molar content up to 60%, the sulphur in the gas that gasifies is mainly H2S is conducive to the recycling of sulphur.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (12)
1. a kind of processing method of heavy petroleum hydrocarbon, this method, which is included in, faces under hydrogen or conditions of non-hydrogen, by heavy petroleum hydrocarbon with
Contact agent transmission of heat by contact in contact cracker, makes heavy petroleum hydrocarbon be in contact cracking reaction, will contact cracking reaction
Generate can distillate distillated out of reactor after be cooled in 0.5s 350 DEG C hereinafter, the contact agent by aluminium oxide and
Magnesia forms, and the specific surface area of the contact agent is 50-150m2/ g, Kong Rongwei 0.05-0.4cm3/ g, thermal coefficient 20-
The shape of 50W/ (mK), the contact agent are microballoon shape, and average grain diameter is 50-75 μm, and particle size range is 20-200 μm,
On the basis of the total amount of the contact agent, the content of aluminium oxide is 20-80 weight %, and the content of magnesia is 20-80 weight %.
2. processing method according to claim 1, wherein the thermal coefficient of the contact agent is 25-37W/ (mK).
3. processing method according to claim 1, wherein the magnesia is foramen magnum-mesoporous magnesia, the aperture of macropore
For 50-100nm, mesoporous aperture is 15-50nm.
4. processing method according to claim 1, wherein under conditions of non-hydrogen, the condition for contacting cracking reaction includes
450-650 DEG C of reaction temperature, weight (hourly) space velocity (WHSV) 1-100h-1, the mass ratio of contact agent and heavy oil feedstock is 1-30：1, contact cracking is anti-
Answer gas phase residence time 0.5-2.0s in device, the mass ratio of vapor and heavy oil feedstock is 0.05-1：1；
Under hydro condition, the condition for contacting cracking reaction includes 450-650 DEG C of reaction temperature, weight (hourly) space velocity (WHSV) 1-100h-1, contact
The mass ratio of agent and heavy oil feedstock is 1-30：1, the mass ratio of vapor and heavy oil feedstock is 0.05-1：1, gross pressure 0-
1MPa, hydrogen partial pressure 0.1-0.5MPa, hydrogen-oil ratio 10-1500m3/m3, contact cracker in the gas phase residence time be
0.5-4.0s。
5. processing method according to claim 4, wherein the heavy petroleum hydrocarbon is heated to the heating speed of reaction temperature
Rate is 20-500 DEG C/s.
6. processing method according to claim 1, wherein the carbon residue of the heavy petroleum hydrocarbon is 10-45 weight %, gold
Category content is 25-1000 μ g/g.
7. processing method according to claim 1, wherein gas residence time is 1.0-10 seconds, the gasification temperature of dense bed
Degree is 600-950 DEG C, and the linear velocity of dense bed is 0.2-0.6m/s.
8. processing method according to claim 1, wherein oxygen mole fraction is 5%-30% in gasifying agent, remaining is
The mixture of nitrogen or vapor or carbon dioxide or two or more in them.
9. processing method according to claim 8, wherein oxygen mole fraction is 5%-20% in gasifying agent.
10. processing method according to claim 9, wherein the sulphur in gasification gas is mainly with H2The form of S and COS exists.
11. processing method according to claim 10, wherein H in gasification gas2S and COS accounts for 99.0 of total sulfur in gasification gas
Volume % or more.
12. according to the processing method described in any one of claim 1-11, wherein this method further includes that gained gasifies gas
It is sent into sulfur recovery unit and removes sulphur, the gasification gas after gained desulfurization is after Water gas shift/WGS device, isolated hydrogen and CO2Or
Fuel gas application is used as after person's desulfurization, or for generating electricity or steam occurring as boiler oil.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260529A (en) * | 2010-05-27 | 2011-11-30 | 中国石油化工股份有限公司 | Combined method for processing inferior heavy oil |
| CN102260528A (en) * | 2010-05-27 | 2011-11-30 | 中国石油化工股份有限公司 | Heavy oil processing composition method for improving liquid yield |
| CN103789013A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Metal chelating agent, preparation method and application thereof, and catalytic cracking method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260529A (en) * | 2010-05-27 | 2011-11-30 | 中国石油化工股份有限公司 | Combined method for processing inferior heavy oil |
| CN102260528A (en) * | 2010-05-27 | 2011-11-30 | 中国石油化工股份有限公司 | Heavy oil processing composition method for improving liquid yield |
| CN103789013A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Metal chelating agent, preparation method and application thereof, and catalytic cracking method |
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