CN105498818B - 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 the present invention relates to contact agent and using contact agent processing heavy petroleum hydrocarbon, the contact agent contain carborundum and magnesia.The contact agent has high thermal conductivity, the contact cracking reaction of high reaction temperature, short residence time can be realized during fluid bed or riser processing 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 developing rapidly for global economy, the demand of the energy is increasingly increased, and petroleum resources are short, international oil price
High, petroleum resources poor quality, heaviness and environmental requirement increasingly strictly propose higher requirement for oil Refining Technologies：Heavy
The efficient green conversion of oil.On the one hand require " to eat dry squeeze only " as far as possible to feedstock oil, on the other hand seek to save.
At present, the catalytic cracking of heavy oil, fluidisation are included with fluid bed or riser processing heavy, the technique of inferior feedstock oil
Coking, flexicoking etc. are increasingly subject to pay attention to.During 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 carry charcoal contact agent and enter again
Raw unit is regenerated, and this process occurs two under the high temperature conditions by pyrolytic cracking and short residence time to suppress crackate
Secondary cracking reaction, to obtain the liquid yield and less coke and dry gas yied of maximum.Such technique is carried out both at home and abroad
Substantial amounts of research, develops various short residence time process, such as the rapid cleavage technique that this company of stone weber develops, its
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 its patentability is special reaction
Cell structure is advantageous to raw material and regenerative agent, and mixing reaches high reaction temperature rapidly.Contact agent in such technology contains with catalysis
The catalyst of activity, inert quartz sand, coke, the calcined kaolin etc. of low specific surface area.These technologies are all with corresponding
Patent equipment reaches high reaction temperature and short residence time, the thermal conductivity of catalyst carrier or catalyst in itself to course of reaction
Matter is simultaneously not concerned with.
The content of the invention
Connect it is an object of the invention 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.
Carborundum high mechanical strength, heat endurance and good heat-transfer, as a kind of semi-conducting material, structural ceramics and increasing
Strong material causes the extensive concern of people already, but is not yet attracted people's attention as catalysis material.The present inventor
It was found that using the material for containing carborundum and magnesia as contact agent, made using existing fluid bed or riser reactor
High liquid yield and relatively low dry gas, coke yield can be obtained for contact cracker, so as to substantially reduce to equipment
Requirement.
According to an aspect of the present invention, the invention provides a kind of contact agent, the contact agent to contain carborundum and magnesia.
According to another aspect of the present invention, the invention provides a kind of processing method of heavy petroleum hydrocarbon, this method to include
In the case where facing hydrogen or conditions of non-hydrogen, heavy petroleum hydrocarbon is being contacted into transmission of heat by contact in cracker with contact agent, is making heavy stone
Petroleum hydrocarbon is in contact cracking reaction, it is characterised 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, so that complicated as technology without being carried out to equipment when being used to process 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 the heavy oil of routine is fixed fluidized bed
83.12% liquid yield, and as little as 1.27% and 15.48% dry gas, coke yield.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
According to an aspect of the present invention, the invention provides a kind of contact agent, the contact agent to contain carborundum and magnesia.
Under preferable case, on the basis of the total amount of the contact agent, the content of carborundum is 10-99 weight %, magnesia
Content be 1-90 weight %.In the case of further preferably, on the basis of the total amount of the contact agent, the content of carborundum is
20-80 weight %, the content of magnesia is 20-80 weight %.
According to one embodiment of the present invention, contact agent of the invention, which also contains, is no more than the preferred 5-30 weights of 30 weight %
Measure % more preferably 10-30 weight % binding agents.The binding agent is preferably aluminum oxide or Alumina gel.
In the case of further preferably, on the basis of the total amount of the contact agent, the content of carborundum is 50-90 weight %,
The content of magnesia is respectively 1-40 weight %, and the content of binding agent is 5-30 weight %.Obtained using above-mentioned preferred content proportioning
The contact agent obtained, which carries out contact cracking, can further improve liquid yield, reduce coke and dry gas yied.
In the case of further preferably, the specific surface area of the contact agent is more than or equal to 90m2/ g, pore volume 0.2-1cm3/g。
In the case of still more preferably, the specific surface area of the contact agent is 90-120m2/ g, pore volume 0.2-0.5cm3/g.It can pass through
Select suitable carborundum and magnesia and suitably adjust ratio therebetween to obtain said structure parameter.Above-mentioned
Under the conditions of preferable specific surface area and pore volume, the quality of liquid oil can be further improved.It is preferably fluidity in order to obtain
Energy and abrasion resistance properties, preferably described contact agent profile are microballoon shape, and the average grain diameter of the further preferred contact agent is
50-75 μm, the particle size range of still more preferably described contact agent is 20-200 μm.
In the case of further preferably, the thermal conductivity factor of the contact agent is 25-93W/ (mK), preferably 30-70W/ (m
K).In above-mentioned preferred scope, contact agent has good heat conductivility in itself, so as in the contact agent and heavy oil petroleum hydrocarbon
When being contacted in fluid bed or riser reactor, contact agent can be more quickly by self-contained heat transfer to contact agent
Surface oil reservoir, and make oil reservoir that thermal cracking occur in higher temperature, thermal cracking lighter products fast transfer to gas phase, prevent secondary
The generation of cracking reaction, so as to reduce the yield of coke and dry gas.
In the present invention, unless otherwise indicated, specific surface area and pore volume are automatically compared using Quantachrome companies AS-6
Surface area and lacunarity analysis instrument, determined by static state low temperature capacity sorbent method, be calculated according to BET equations；Thermal conductivity factor 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, there is preferable abrasion resistance and higher thermal conductivity factor, in contact cracking process
Middle heat carrier and coke carrier and fluidizing reagent as cracking process, can be within the most short 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
Fluid bed or riser using high reaction temperature and short contacting time as principal character are processed in heavy petroleum hydrocarbon method.
Carborundum in contact agent provided by the invention can be the silicon carbide micro-powder that any mode of production provides.It is preferred that institute
The average grain diameter for stating carborundum is 10-70 μm.
It is preferred that the average grain diameter of the magnesia is 10-70 μm, and particle size range is in 20-200 μ ms.Due to existing
Magnesia either to be powdered or be graininess of the particle diameter more than 200 μm, in order to obtain particle diameter within the above range
Magnesium oxide particle, it is of the invention by carrying out mist projection granulating after being beaten existing magnesium oxide particle or powder together with magnesium chloride,
Then it is calcined.The weight ratio preferably 1000 of magnesium oxide particle or powder and magnesium chloride：10-200, preferably 1000：50-100, oxygen
Change the weight ratio preferably 1000 of magnesium granules or powder and the water of mashing：500-1000.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 bar
Part is known to those skilled in the art, will not be repeated here.
In the case of further preferably, in order to obtain higher liquid yield, the pore volume of the magnesia is 0.4-0.6cm3/
g。
The preparation method of contact agent provided by the invention is simple, can be by micro- by the appropriate carborundum of particle diameter and magnesia
The direct mechanical mixture of powder obtains.When the contact agent also contains binding agent, contact agent provided by the invention can also pass through by
Silicon carbide micro-powder and fine magnesium oxide micro-powder add water to be beaten with binding agent, then spray-dried, roasting obtains finished product.Specific preparation process
It is as follows：
(1) silicon carbide micro-powder of the particle size range at 0.1 μm -100 μm is subjected to mechanical mixture with fine magnesium oxide micro-powder.
(2) add Alumina gel into mixture obtained by step (1) and deionized water is beaten to obtain solid content in 20-50
Weight % slurries, wherein Alumina gel account for 5-30 weight %.
(3) slurries obtained by step (2) are spray-dried, carrying out being calcined 0.5-2 hours at 500-800 DEG C can obtain into
Product.
According to another aspect of the present invention, present invention also offers a kind of processing method of heavy petroleum hydrocarbon, this method bag
Include 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 in contact cracking
Reaction, it is characterised in that the contact agent is the contact agent of the above-mentioned offer 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, contact gas phase in cracker and stop
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 dividing potential drop 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 also include by generation can distillate out of reactor
Rapid cooling, the contact agent to be generated that depositing has coke enter gasification unit after distillating.Under preferable case, generation can distillate it is excellent
Choosing is cooled to less than 350 DEG C 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 make product characteristicses stable.
In gasification unit, contact agent to be generated obtained by contact cracking reaction enters in fluidized-bed gasifier, is containing oxygen
In the presence of gasifying agent, make the charcoal on contact agent and gasifying agent reaction, obtain regenerating contact agent and 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 is 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 H2S and COS form is present.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, so as to be easily recycled sulphur, entirely
Technical process environmental protection.
In the case of further preferably, processing method of the invention also includes gasification pneumatic transmission entering sulfur recovery unit removing sulphur,
And by the gasification gas after desulfurization after Water gas shift/WGS device carries out Water gas shift/WGS, isolated hydrogen and CO2Or will be de-
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, it is that gasification gas enters a COS removing means, the COS first
COS can be converted into H by removing means2The further Recovered sulphur of S, COS can also be absorbed and reclaim 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
COS can be converted into H by method2S.Porous solid material CO absorption S can also be used it is enriched with the surface of solids, go forward side by side one
Step obtains COS.From H2The method of S Recovered sulphur refers to the method industrially commonly used, such as claus process.
Compared with prior art, the beneficial effects are mainly as follows the following aspects：
First, contact agent thermal conductivity factor of the invention is high, therefore can be easily achieved being brought rapidly up for feedstock oil, makes liter
Warm speed reduces liquid phase reactor, reduces secondary response, reduce coke and dry gas yied, selectively up to 20~500 DEG C/s
Be stripped of intrinsic coke precursor.
Secondly, the boring ratio of the contact agent is larger, reduces generation massive particles in cracker, makes fluidisation smooth,
Reduce the various inner members in cracker, reduce 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
Rationally using two aspects, while producing light oil, coke more than needed is gasified in gasifier, (CO+ is rich in gained gasification gas
H2), this partial gasification gas can use as fuel gas, may also be used for transformation and hydrogen production, may also be used for generating electricity or produce steaming
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
One or more in oil, deasphalted oil.
The present invention is further illustrated below by embodiment, but and is not so limited present disclosure.
Embodiment 1-5 and comparative example 1-3 is used to prepare contact agent.
Comparative example 1
Black silicon carbide micro mist (offer of Shandong Weifang Yong Hao silicon carbide micro-powders Co., Ltd) is sieved, utilizes laser grain
Degree instrument tests 65 μm of its average grain diameter, and particle size range is at 20 μm -200 μm.Numbering is D1, and composition and physical property are shown in Table 1.
Comparative example 2
By 1000g macropores magnesia (thickness Dehua, Shandong Weifang work, particle diameter be 20-200 μm, average grain diameter be 63 μm) with
800g deionized waters stir, and continuously add 80g magnesium chlorides under agitation, 40min are stirred, by slurries in spray-drying installation
Upper spray drying, be then calcined 5 hours at 600 DEG C, obtain contact agent, numbering D2, particle size range at 20 μm -200 μm,
Composition and physical property are shown in Table 1.
Embodiment 1
By the magnesia contact agent in mass ratio 80 in the silicon carbide contact agent in comparative example 1 and comparative example 2：20 ratio
It is well mixed with the method for machinery, numbering A1, composition and physical property are shown in Table 1.
Embodiment 2
By the magnesia contact agent in mass ratio 20 in the silicon carbide contact agent in comparative example 1 and comparative example 2：80 ratio
It is well mixed with the method for machinery, numbering A2, composition and physical property are shown in Table 1.
Embodiment 3
The high-specific surface area carborundum micro mist prepared using the method disclosed in CN1401564A.Take 1kg silicon carbide micro-powders
(particle diameter is 10-100 μm, and average grain diameter is 41 μm, pore volume 0.6cm with 1kg magnesia3/ g), 4kg deionized waters are added,
Stir, add 0.4kg Alumina gels (production of Shandong catalyst plant), stir 20 minutes, spray shaping, particle mean size 65
μm, particle size range is at 20 μm -200 μm.It is calcined at 600 DEG C and obtains within 60 minutes sample, numbering A3, composition and physical property is shown in
Table 1.
Embodiment 4
Method according to embodiment 3 prepares contact agent, unlike, magnesia is 0.2cm using pore volume3/ g oxidation
Magnesium, obtains contact agent, numbering A4, and composition and physical property are shown in Table 1.
Comparative example 3
Kaolin (Suzhou carclazyte) and boehmite (Shandong Aluminum Plant life master) is levigate, and average grain diameter is 1.0 μm.Take
6kg kaolin, 12kg deionized waters are added, stirred 30 minutes.1.5kg boehmites are taken, 2.25kg deionized waters is added, stirs
Mix uniformly, add nitric acid and adjust pH value to 1.5.Two kinds of slurries are mixed 30 minutes, spray shaping, are calcined at 600 DEG C
Sample is obtained within 60 minutes, numbering D3, for 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 |
| Carborundum, % | 70 | 15 | 41.7 | 41.7 | 100 | 0 | - |
| Magnesia, % | 30 | 80 | 41.7 | 41.7 | 0 | 100 | - |
| Binding agent, % | 0 | 0 | 16.7 | 16.7 | 0 | 0 | - |
| Thermal conductivity factor (W/mK) | 62 | 34 | 48 | 47 | 68 | 25 | 20 |
| Specific surface area (m2/g) | 95 | 102 | 100 | 97 | 93 | 104 | 37 |
| Pore volume (mL/g) | 0.442 | 0.327 | 0.278 | 0.198 | 0.189 | 0.361 | 0.104 |
| Average grain diameter (μm) | 66 | 64 | 65 | 65 | 63 | 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.Urge
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
| Contact agent is numbered | A1 | A2 | A3 | A4 | D1 | D2 | D3 |
| Material balance, m% | |||||||
| H2S | 0.13 | 0.21 | 0.11 | 0.13 | 0.38 | 0.08 | 0.61 |
| Dry gas | 1.27 | 1.64 | 1.33 | 1.54 | 1.16 | 1.85 | 2.35 |
| Liquefied gas | 1.39 | 1.86 | 1.75 | 1.74 | 0.99 | 2.21 | 4.3 |
| C5+ gasoline | 8.15 | 9.87 | 9.04 | 7.14 | 7.45 | 10.56 | 17.85 |
| Diesel oil | 21.76 | 22.27 | 22.93 | 20.47 | 21.33 | 22.78 | 23.77 |
| Heavy oil | 51.82 | 48.11 | 48.90 | 52.86 | 54.52 | 46.28 | 31.01 |
| Coke | 15.48 | 16.04 | 15.94 | 16.12 | 15.16 | 16.24 | 20.11 |
| It is total | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Liquefaction, m% | 83.12 | 82.11 | 82.62 | 82.21 | 83.30 | 81.83 | 76.93 |
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) 6 percentage points are improved, coke yield have dropped more than 4 percentage points.
Embodiment 9
It will number that the contact agent and the carbon residue that are A1 are 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 bar 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.Generation can distillate distillated out of reactor after
Less than 350 DEG C are cooled in 0.5s.The coke content of gained spent agent contact agent containing charcoal (spent agent) is 1.2 weight %.
Dry gas yied is 1.0% in gained crackate, coke yield 12.15%, and it is 86.85% that liquid, which is received,.Green coke because
Sub- coke/carbon residue is 0.81.
Spent agent enters gasifier after stripping.Gas linear velocity is 0.25m/s in dense bed, 620 DEG C of temperature, is passed through
Oxygen-containing 12.3% (mole), the gas of vapor 87.7% (mole), gas residence time 1.5 seconds.(CO+H in gasification gas2)/
CO2Mol ratio be 1.15, gasify gas in (butt) (CO+H2) molar content reach nearly 54.3%, H2S accounts for total sulfur in gasification gas
95.0% (volume), COS account for gasification gas in total sulfur 4.5% (volume).Contact agent after regeneration is returned in cracker.
Embodiment 10
It will number that the contact agent and the carbon residue that are A2 are 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 bar 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.Generation can distillate distillated out of reactor after
Less than 350 DEG C are cooled in 0.5s.The coke content of gained spent agent contact agent containing charcoal (spent agent) is 2.1 weight %.
Dry gas yied is 1.1% in gained crackate, coke yield 15.02%, and it is 83.88% that liquid, which is received,.Green coke because
Sub- coke/carbon residue is 0.83.
Spent agent enters gasifier after stripping.Gas linear velocity is 0.12m/s in dense bed, 680 DEG C of temperature, is passed through
Air, gas residence time 5 seconds.(CO+H in gasification gas2)/CO2Mol ratio be 1.21, gasify gas in (butt) (CO+H2)
Molar content reaches nearly 55.1%, H2S accounts for 93.5% (volume) of total sulfur in gasification gas, and COS accounts for 4.1% of total sulfur in gasification gas
(volume).Contact agent after regeneration is returned in cracker.
Embodiment 11
It will number that the contact agent and the carbon residue that are A3 are 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 bar 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.Generation can distillate distillated out of reactor after
Less than 350 DEG C are cooled in 0.5s.The coke content of gained spent agent contact agent containing charcoal (spent agent) is 1.5 weight %.
Dry gas yied is 1.4% in gained crackate, coke yield 29.4%, and it is 69.2% that liquid, which is received,.The green coke factor
Coke/carbon residue is 0.84.
Spent agent enters gasifier after stripping.Gas linear velocity is 0.40m/s in dense bed, 560 DEG C of temperature, is passed through
Oxygen-containing 30% (mole), vapor 40% (mole), the gas of carbon dioxide 30% (mole), gas residence time 50 seconds.Gas
Change (CO+H in gas2)/CO2Mol ratio be 1.50, gasify gas in (butt) (CO+H2) molar content reach nearly 57.4%, H2S
96.3% (volume) of total sulfur in gasification gas is accounted for, COS accounts for 3.8% (volume) of total sulfur in gasification gas.Contact agent after regeneration returns
Return in cracker.
Embodiment 12
It will number that the contact agent and the carbon residue that are A1 are 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 bar 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 dividing potential drop is
0.1MPa, hydrogen-oil ratio 1000m3/m3.Generation 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 1.0 weight %.
Dry gas yied is 1.20% in gained crackate, coke yield 12.23%, and it is 86.57% that liquid, which is received,.
Green coke factor coke/carbon residue is 0.81.
Spent agent enters gasifier after stripping.Gas linear velocity is 0.25m/s in dense bed, 620 DEG C of temperature, is passed through
Oxygen-containing 12.3% (mole), the gas of vapor 87.7% (mole), gas residence time 1.5 seconds.(CO+H in gasification gas2)/
CO2Mol ratio be 1.38, 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 is returned in cracker.
Embodiment 13
It will number that the contact agent and the carbon residue that are A2 are 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 bar 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
The heating rate for answering temperature is 120 DEG C/s, and the gas phase residence time is 1.75s, and gross pressure (gauge pressure) is 0.8MPa, and hydrogen dividing potential drop is
0.3MPa, hydrogen-oil ratio 200m3/m3.Generation 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 1.5 weight %.
Dry gas yied is 1.21% in gained crackate, coke yield 15.38%, and it is 83.41% that liquid, which is received,.
Green coke factor coke/carbon residue is 0.85.
Spent agent enters gasifier after stripping.Gas linear velocity is 0.20m/s in dense bed, 680 DEG C of temperature, is passed through
Oxygen-containing 22.3% (mole), the gas of vapor 77.7% (mole), gas residence time 3 seconds.(CO+H in gasification gas2)/CO2
Mol ratio be 1.23, H2S accounts for 94.4% (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 is returned in cracker.
Embodiment 14
It will number that the contact agent and the carbon residue that are A3 are 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 bar 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
The heating rate for answering temperature is 120 DEG C/s, and the gas phase residence time is 1.75s, and gross pressure (gauge pressure) is 0.7MPa, and hydrogen dividing potential drop is
0.2MPa, hydrogen-oil ratio 400m3/m3.Generation 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 2.0 weight %.
Dry gas yied is 1.25% in gained crackate, coke yield 29.4%, and it is 69.35% that liquid, which is received,.
Green coke factor coke/carbon residue is 0.84.
Spent agent enters gasifier after stripping.Gas linear velocity is 0.20m/s in dense bed, 680 DEG C of temperature, is passed through
Oxygen-containing 22.3% (mole), the gas of vapor 77.7% (mole), gas residence time 3 seconds.(CO+H in gasification gas2)/CO2
Mol ratio be 1.30, H2S accounts for 95.0% (volume) of total sulfur in gasification gas, and COS accounts for 4.3% (body of total sulfur in gasification gas
Product).Contact agent after regeneration is returned in cracker.
Comparative example 7
Be 35.0 weight % by magnesia (identical with the source of embodiment 3) and carbon residue, metal be 550 μ g/g, sulfur content
Cracking reaction is in contact 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.Generation can distillate distillated out of reactor after be cooled in 0.5s
Less than 350 DEG C.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%, 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, 680 DEG C of temperature, is passed through
Oxygen-containing 22.3% (mole), the gas of vapor 77.7% (mole), gas residence time 3 seconds.(CO+H in gasification gas2)/CO2
Mol ratio be 1.38, 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 is returned 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 0.85 percentage point, coke reduces 11.9 percentage points, and liquid, which is received, improves 12.75 percentage points, together
When gasify gas in (butt) (CO+H2) molar content up to 60%, the sulphur in the gas that gasifies is mainly H2S, be advantageous to the recovery of sulphur.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, 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 equally be considered as content disclosed in this invention.
Claims (20)
1. a kind of contact agent, the contact agent contains carborundum and magnesia；On the basis of the total amount of the contact agent, carborundum
Content is 10-99 weight %, and the content of magnesia is 1-90 weight %.
2. contact agent according to claim 1, wherein, on the basis of the total amount of the contact agent, the content of carborundum is
20-80 weight %, the content of magnesia is 20-80 weight %.
3. contact agent according to claim 1, wherein, the thermal conductivity factor of the contact agent is 25-93W/ (mK).
4. contact agent according to claim 1, wherein, the thermal conductivity factor of the contact agent is 30-70W/ (mK).
5. according to the contact agent described in any one in claim 1-4, wherein, specific surface area >=90m of the contact agent2/ g, hole
Hold for 0.2-1cm3/g。
6. according to the contact agent described in any one in claim 1-4, wherein, the specific surface area of the contact agent is 90-120m2/
G, pore volume 0.2-0.5cm3/g。
7. according to the contact agent described in any one in claim 1-4, wherein, the profile of the contact agent is microballoon shape,
Average grain diameter is 50-75 μm, and particle size range is 20-200 μm.
8. according to the contact agent described in any one in claim 1-4, wherein, the average grain diameter of the carborundum is 10-70 μ
M, the pore volume of the magnesia is 0.4-0.6cm3/g。
9. 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, it is characterised in that described
Contact agent is the contact agent described in any one in claim 1-8.
10. processing method according to claim 9, wherein, under conditions of non-hydrogen, contacting the condition of 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, contacting the condition of 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 dividing potential drop 0.1-0.5MPa, hydrogen-oil ratio 10-1500m3/m3, contact cracker in the gas phase residence time be
0.5-4.0s。
11. processing method according to claim 10, wherein, the heavy petroleum hydrocarbon is heated to the heating of reaction temperature
Speed is 20-500 DEG C/s.
12. processing method according to claim 9, wherein, the carbon residue of the heavy petroleum hydrocarbon is 10-45 weight %,
Tenor is 25-1000 μ g/g.
13. processing method according to claim 9, wherein, this method also includes that evaporating for cracking reaction generation will be contacted
Go out and be cooled to less than 350 DEG C after thing distillates out of reactor in 0.5s.
14. processing method according to claim 13, wherein, this method also includes that the contact agent to be generated for having coke will be deposited
It is sent into fluidized-bed gasifier, in the presence of the gasifying agent containing oxygen, the charcoal on contact agent is reacted with gasifying agent, obtain again
Give birth to contact agent and rich in CO, H2Gasification gas, reaction condition is the 0.5-60 seconds including gas residence time in fluidized-bed gasifier,
The gasification temperature of dense bed is 550-1000 DEG C, and the linear velocity of dense bed is 0.05-0.6m/s.
15. processing method according to claim 14, wherein, when reaction condition includes gas stop in fluidized-bed gasifier
Between be the 1.0-10 seconds, the gasification temperature of dense bed is 600-950 DEG C, and the linear velocity of dense bed is 0.2-0.6m/s.
16. processing method according to claim 15, wherein, oxygen mole fraction is 5%-30% in gasifying agent, remaining
For nitrogen or vapor or carbon dioxide, or the mixture of two or more in them.
17. processing method according to claim 16, wherein, oxygen mole fraction is 5%-20% in gasifying agent.
18. according to the processing method described in any one in claim 14-17, wherein, the sulphur in the gas that gasifies is mainly with H2S and
COS form is present.
19. processing method according to claim 18, wherein, H in the gas that gasifies2S and COS accounts for 99.0 of total sulfur in gasification gas
More than volume %.
20. according to the processing method described in any one in claim 14-17, wherein, this method also includes gasifying gained
Pneumatic transmission enters sulfur recovery unit removing sulphur, and the gasification gas after gained desulfurization is after Water gas shift/WGS device, isolated hydrogen and CO2
Either as fuel gas application or for generating electricity or steam occurring as boiler oil after desulfurization.
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