CN105586068A - Contact agent and processing method of heavy petroleum hydrocarbon - Google Patents
Contact agent and processing method of heavy petroleum hydrocarbon Download PDFInfo
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- CN105586068A CN105586068A CN201410557771.0A CN201410557771A CN105586068A CN 105586068 A CN105586068 A CN 105586068A CN 201410557771 A CN201410557771 A CN 201410557771A CN 105586068 A CN105586068 A CN 105586068A
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Abstract
The invention relates to a contact agent and a method for processing heavy petroleum hydrocarbon by the use of the contact agent. The contact agent is composed of aluminium oxide and magnesium oxide. The contact agent has high coefficient of thermal conductivity and can realize a contact cracking reaction with high reaction temperature and short residence time during the process of processing heavy petroleum hydrocarbon in a fluidized bed or a riser, so as to effectively raise yield of a liquid and reduce yield of dry gas and coke.
Description
Technical field
The present invention relates to a kind of contact agent and use the processing method of the heavy petroleum hydrocarbon of this contact agent.
Background technology
Along with developing rapidly of global economy, the demand of the energy is increased day by day, and petroleum resources shortage,International oil price is high, petroleum resources are inferior, heaviness and environmental requirement increasingly stringent are oil Refining TechnologiesHave higher requirement: the efficient green of mink cell focus transforms. Require to feedstock oil as much as possible on the one hand" eating dry squeezing only ", is exactly energy-conservation on the other hand.
At present, comprise the catalysis of heavy oil with the technique of fluid bed or riser processing heavy, inferior feedstock oilCracking, fluid coking, flexicoking etc. come into one's own day by day. When this type of processes mink cell focus, fluidisationMedium is not only as catalytic center, and the while is as the carrier of heat and coke.
Thermocracking process taking high reaction temperature, short residence time as feature is in heavy oil modification, catalytic crackingThere is application Deng numerous areas. Using fluid bed or riser during as reactor processing heavy oil feedstock oil,Feedstock oil sprays at a high speed by nozzle, fast reaction after contact with thermo-contact agent, the light petroleum gas of generation andContact agent separates fast, enters regeneration unit and regenerates and carry a charcoal contact agent, and this process is by high anneal crackChange and short residence time suppress crackate secondary cracking reaction occur under hot conditions, to obtainLarge liquid yield and less coke and dry gas yied. Carry out a large amount of grinding with regard to this type of technique both at home and abroadStudy carefully, developed various short residence time cracking technique, as the quick cracking work of this company's exploitation of stone weberSkill, its patent shows and can select thermophore according to raw material and target product; IvanhoeEnergyInc. exploitationHLT technique; The fluid catalytic cracking technology that Dao Daer proposes, this process reactor belongs to lower fluidisationBed bioreactor, its patentability is that special reaction chamber structure is conducive to raw material and regenerative agent mixes and reaches rapidlyHigh reaction temperature. Contact agent in this type of technology contains the catalyst with catalytic activity, the quartz of inertiaThe calcined kaolin of sand, coke, low specific surface area etc. These technology are all to come with corresponding patent equipmentReach high reaction temperature and short residence time, the heat conduction of the catalyst carrier to course of reaction or catalyst itselfCharacter is not paid close attention to.
Summary of the invention
The object of the present invention is to provide a kind of new contact agent that can significantly improve liquid yield andUse the processing method of the heavy petroleum hydrocarbon of this contact agent.
Aluminium oxide mechanical strength is high, and heat endurance and good heat-transfer obtain as the carrier of catalysis materialTo extensively quoting. The present inventor finds, uses and contains aluminium oxide and magnesian material as connecingTouch agent, use existing fluid bed or riser reactor can obtain high as contact crackerLiquid yield and lower dry gas, coke yield, thus the requirement to equipment greatly reduced.
According to an aspect of the present invention, the invention provides a kind of contact agent, this contact agent by aluminium oxide andMagnesia.
According to a further aspect in the invention, the invention provides a kind of processing method of heavy petroleum hydrocarbon, shouldMethod is included in faces under hydrogen or conditions of non-hydrogen, and heavy petroleum hydrocarbon is being contacted to cracker with contact agentInterior transmission of heat by contact, makes heavy petroleum hydrocarbon come in contact cracking reaction, it is characterized in that, described contact agent isAbove-mentioned contact agent provided by the invention.
Contact agent provided by the invention is transferring heat energy fast, can be in order to realize high reaction temperature, shortThe time of staying is the heat cracking reaction of feature, thus when processing heavy, inferior raw material without to equipmentThe complicated improvement of carrying out as technology can be produced more light-end products and minimum coke and dry gas. ExampleAs, can find out from following embodiment 1, use contact agent provided by the invention to connect inferior heavy oilTouch cracking, in conventional heavy oil is fixed fluidized bed, can obtain the liquid yield up to 81.01%, andBe low to moderate 1.77% and 17.01% dry gas, coke yield. Trace it to its cause, may be because:
(1) contact agent has the function of quick conductive as heat carrier, and thermal cracking lighter products is turned fastMove to gas phase, prevent the generation of secondary cracking reaction, reduce the productive rate of coke and dry gas;
(2) contact agent itself, without catalytic cracking activity, prevents residual oil overcracking;
(3) contact agent has larger duct, is more suitable for the transfer of slag oil cracking product coke.
Other features and advantages of the present invention are described in detail the detailed description of the invention part subsequently.
Detailed description of the invention
Below the specific embodiment of the present invention is elaborated. Should be understood that, retouch in this placeThe detailed description of the invention of stating only, for description and interpretation the present invention, is not limited to the present invention.
According to an aspect of the present invention, the invention provides a kind of contact agent, this contact agent by aluminium oxide andMagnesia composition.
Under preferable case, taking the total amount of described contact agent as benchmark, the content of aluminium oxide is that 20-80 is heavyAmount %, magnesian content is 20-80 % by weight.
Under preferable case, the specific area >=10m of this contact agent2/ g, pore volume is 0.05-0.5cm3/ g. EnterUnder one step preferable case, the specific area of this contact agent is 50-150m2/ g, pore volume is 0.05-0.4cm3/g。Can obtain by the ratio of selecting suitable aluminium oxide and magnesia and suitably adjust between the twoObtain said structure parameter. Under above-mentioned preferred specific area and pore volume condition, can further improve liquidThe quality of body oil product.
Due to existing magnesia or be Powdered,, or be the graininess of particle diameter more than 200 μ m,In order to obtain the magnesium oxide particle of particle diameter in above-mentioned scope, the present invention passes through existing magnesium oxide particleOr powder carries out mist projection granulating, then roasting after pulling an oar together with magnesium chloride. Magnesium oxide particle or powder andThe weight ratio of magnesium chloride is preferably 1000:10-200, preferably 1000:50-100, magnesium oxide particle or powderEnd is preferably 1000:500-1000 with the weight ratio of magnesium chloride. The temperature of roasting can be 400-800 DEG C,Preferably 500-700 DEG C, the time of roasting can be 2-8 hour, is preferably 4-6 hour. Mist projection granulatingConcrete operations and condition have been conventionally known to one of skill in the art, do not repeat them here.
Further, under preferable case, in order to obtain higher liquid yield, described magnesia is foramen magnum-mesoporousMagnesia, the aperture of macropore is 50-100nm, mesoporous aperture is 15-50nm. Wherein macropore accounts for 20-50Volume %, the mesoporous 30-50 volume % that accounts for.
Equally, due to existing aluminium oxide or be Powdered, or be particle diameter more than 200 μ mGranular, in order to obtain the alumina particle of particle diameter in above-mentioned scope, the present invention passes through existing oxidationAlumina particles or powder carry out mist projection granulating after pulling an oar together with aluminium colloidal sol, then roasting. Alumina particle orThe weight ratio of powder and aluminium colloidal sol is preferably 1-10:1, preferably 3-8:1, alumina particle or powder andThe weight ratio of the water of making beating use is preferably 2-5:1. The temperature of roasting can be 400-800 DEG C, preferably500-700 DEG C, the time of roasting can be 2-8 hour, is preferably 4-6 hour. Mist projection granulating concreteOperation and condition have been conventionally known to one of skill in the art, do not repeat them here.
In the present invention, the aluminium oxide in described contact agent can be that any presoma is as amorphous hydrogen-oxygenChange aluminium, boehmite, boehmite etc. are prepared from by spray roasting mode, described oxidationAluminium can be α-Al2O3、γ-Al2O3、θ-Al2O3In one or more.
In order to obtain better fluidizing performance and abrasion resistance properties, preferred described contact agent profile is microspheroidalShape, further the average grain diameter of preferred described contact agent is 50-75 μ m, further preferred described contactThe particle size range of agent is 20-200 μ m.
The thermal conductivity factor of aluminium oxide is at 25～34W/ (mK), and magnesian thermal conductivity factor exists25～37W/ (mK), therefore, in the present invention, the thermal conductivity factor of described contact agent is 25-40W/ (mK),Preferably 25-35W/ (mK). In above-mentioned preferable range, contact agent itself has good heat conductivility,Thereby in the time that described contact agent contacts in fluid bed or riser reactor with heavy oil petroleum hydrocarbon, contact agentCan more quickly self-contained heat be passed to contact agent surface oil reservoir, and make oil reservoir higherTemperature generation thermal cracking, thermal cracking lighter products fast transfer, to gas phase, prevents sending out of secondary cracking reactionRaw, thus the productive rate of reduction coke and dry gas.
In the present invention, except as otherwise noted, specific area and pore volume adopt the AS-6 of Quantachrome companyFull-automatic specific area and lacunarity analysis instrument, by static state low temperature capacity determination of adsorption method, according to BETEquation calculates; Thermal conductivity factor uses HotDiskAB company of Sweden to produce thermal constant analyzer, adoptsWith moment state mode record.
Contact agent provided by the invention, has good abrasion resistance and higher thermal conductivity factor, in contactIn cracking process as heat carrier and coke carrier and the fluidizing reagent of cracking process, can be in the shortest timeInterior heat entrained contact agent is transmitted to surperficial oil reservoir, when realizing high reaction temperature and short contactBetween. Contact agent provided by the invention is specially adapted to taking high reaction temperature and short contacting time as principal characterFluid bed or riser processing heavy petroleum hydrocarbon method in.
The preparation method of contact agent provided by the invention is simple, can by by aluminium oxide suitable particle diameter withMagnesia direct mechanical is mixed to get.
According to a further aspect in the invention, the present invention also provides a kind of processing method of heavy petroleum hydrocarbon,The method is included in faces under hydrogen or conditions of non-hydrogen, by heavy petroleum hydrocarbon and contact agent transmission of heat by contact, makes heavilyMatter petroleum hydrocarbon comes in contact cracking reaction, it is characterized in that, described contact agent provides for the present invention is above-mentionedContact agent.
According to the present invention, under conditions of non-hydrogen, the condition of contact cracking reaction preferably includes: reaction temperatureDegree 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, connectsTouch gas phase time of staying 0.5-2.0s in cracker, the mass ratio of steam and heavy oil feedstock is0.05-1：1。
Under hydro condition, the condition of contact 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, steam and heavy oil are formerThe mass ratio of material is 0.05-1:1, and gross pressure is 0-1MPa, and hydrogen dividing potential drop is 0.1-0.5MPa, and hydrogen-oil ratio is10-1500m3/m3, gas phase time of staying 0.5-4.0s in contact cracker. In the present invention, unless specialDo not mentionlet alone brightly, 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, described processing method also comprise by generate can distillate fromIn reactor, distillate rear coolingly rapidly, the contact agent to be generated that deposits coke enters gasification unit. Preferably feelingsUnder condition, can distillate preferably the distillating in reactor of generation, in 0.5s, be cooled to below 350 DEG C.Avoid thus secondary cracking and the condensation reaction of oil gas, reduced device fouling, make product characteristics steady simultaneouslyFixed.
In gasification unit, contact cracking reaction gained contact agent to be generated enters in fluidized-bed gasifier, is containingHave under the gasifying agent of oxygen exists, make charcoal on contact agent and gasifying agent reaction, obtain regenerating contact agent andBe rich in CO, H2Gasification gas. In fluidized-bed gasifier, reaction condition preferably includes: gas residence timeFor 0.5-60 second, be preferably 1.0-10 second. The gasification temperature of dense bed is 550-1000 DEG C, is preferably600-950 DEG C; The linear velocity 0.05-0.6m/s of dense bed, is preferably 0.2-0.6m/s. With prior art phaseRatio, greatly reduces gasification temperature, can not destroy structure and the character of contact agent simultaneously.
Preferably in gasifying agent, oxygen mole fraction is 5%-30%, and all the other are nitrogen or steam or titanium dioxideCarbon, or two or more mixture in them. Oxygen mole fraction in further preferred gasifying agentFor 5%-20%.
Wherein, the sulphur in gasification gas is mainly with H2The form of S and COS exists. On spent agent, coke occursH in the gasification gas that gasification reaction generates2S and COS account for gasification gas in total sulfur 99.0% (volume) withUpper, thus be easy to reclaim sulphur, whole technical process environmental protection.
Further under preferable case, processing method of the present invention also comprises gasification pneumatic transmission is entered to sulfur recovery unitRemove sulphur, and by the gasification gas after desulfurization after Water gas shift/WGS device carries out Water gas shift/WGS, separateTo hydrogen and CO2Or the gasification gas after desulfurization is applied as fuel gas, or be used for generating electricity or conductBoiler oil generation steam.
First removing of sulfur-containing compound to gasification in gas be that gasification gas enters a COS and removes dressPut, described COS removes device can be converted into H by COS2The further Recovered sulphur of S, also can absorbCOS also reclaims COS. It can be that organic amine absorption process, hydrogenation turn that COS removes the method that device adoptsChange method, hydrolysis method, oxidation conversion method, absorption method etc. These methods can be converted into H by COS2S。Also can adopt porous solid material CO absorption S to make it in surface of solids enrichment, and further obtainCOS. From H2The method of S Recovered sulphur refers to industrial conventional method, as claus process etc.
Compared with prior art, beneficial effect of the present invention is mainly reflected in the following aspects:
First, contact agent thermal conductivity factor of the present invention is high, therefore can be easy to realize the rapid of feedstock oilHeat up, make heating rate reach 20～500 DEG C/s, reduced liquid phase reactor, reduced secondary response, reduceCoke and dry gas yied, optionally removed intrinsic coke precursor.
Secondly, the boring ratio of described contact agent is larger, has reduced in cracker and has generated bulk particle, makesFluidisation is smooth and easy, has reduced 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 heavy oil deep processing and superfluous charcoalMatter residue rationally utilizes two aspects, and when producing light oil, the coke of having more than needed gasifies in gasifier,In gained gasification gas, be rich in (CO+H2), this part gasification gas can be used as fuel gas and uses, and also canBe used for transformation and hydrogen production, also can be used for generating or produce steam. CO after these processes are used2Substantially reachTo 100%, can trap, reduce refinery C discharge.
According to the present invention, described heavy petroleum hydrocarbon can be that existing various density is large, carbon residue is high, goldenBelong to and the high inferior oil material of sulfur content, for example, the carbon residue of described heavy petroleum hydrocarbon can be heavy for 10-45Amount %, tenor can be 25-1000 μ g/g. Particularly, described heavy petroleum hydrocarbon can be normal pressure slagOne or more in oil, decompression residuum, visbroken resids, hydrocracking tail oil, deasphalted oil.
Further illustrate the present invention below by embodiment, but therefore do not limit content of the present invention.
Embodiment 1-4 and comparative example 1-3 are for the preparation of contact agent.
Comparative example 1
By even to 3000g macropore boehmite (Shandong Aluminum Plant provides) and 800g deionized water and stirring,(Qilu Petrochemical Company's catalyst plant is produced, and alumina content is under stirring, to continue to add 600g aluminium colloidal sol22.5 % by weight), stir 20min, slurries are sprayed on spray-drying installation dry, then at 600 DEG CRoasting 5 hours, obtains contact agent, is numbered D1, and particle size range, at 20 μ m-200 μ m, forms and thingRationality matter is in table 1.
Comparative example 2
By 1000g macropore magnesia, (thick Dehua, Weifang, Shandong work, particle size range is at 20 μ m-200 μ m, flatAll particle diameter is that 38 μ are m) even with 800g deionized water and stirring, under agitation continues to add 80g magnesium chloride,Stir 40min, slurries are sprayed on spray-drying installation dry, then 600 DEG C of roastings 5 hours,Obtain contact agent, be numbered D2, particle size range is at 20 μ m-200 μ m, and aperture is greater than 50nm and accounts for 25Volume %, the mesoporous 43 volume % that account for of aperture 20nm. Composition and physical property are in table 1.
Embodiment 1
The part by weight that is 8:2 by D1:D2 by the contact agent in comparative example 1 and comparative example 2, makesMix by the mode of mechanical mixture, obtain contact agent, be numbered A1, composition and physical property are shown inTable 1.
Embodiment 2
The ratio that is 2:8 in D1:D2 by the contact agent in comparative example 1 and comparative example 2, use machineThe mode that tool mixes mixes, and obtains contact agent, is numbered A2, and composition and physical property are in table 1.
Embodiment 3
By 3000g macropore boehmite, (Shandong Aluminum Plant provides, and particle size range is at 20 μ m-200 μ m, flatAll particle diameter is that 43 μ are m) even with 800g deionized water and stirring, under agitation continues to add 500g aluminium moltenGlue (Qilu Petrochemical Company's catalyst plant is produced, and alumina content is 25 % by weight), stirs 20min, willSlurries are sprayed dry on spray-drying installation, then, 1000 DEG C of roastings 5 hours, obtain aluminium oxide granuleGrain, particle size range is at 20 μ m-200 μ m, and average grain diameter is 65 μ m, and thermal conductivity factor is 33W/ (mK).
By 1000g macropore magnesia, (thick Dehua, Weifang, Shandong work, particle size range is at 20 μ m-200 μ m, flatAll particle diameter is that 38 μ are m) even with 800g deionized water and stirring, under agitation continues to add 180g chlorinationMagnesium, stirs 40min, slurries is sprayed on spray-drying installation dry, then 800 DEG C of roastings 5Hour, obtaining magnesium oxide particle, particle size range is at 20 μ m-200 μ m, and aperture is greater than the macropore of 50nmAccount for 35 volume %, the mesoporous 37 volume % that account for that aperture is 20nm.
By even by weight 1:1 mechanical mixture to above-mentioned aluminium oxide and magnesia, obtain contact agent, compileNumber be A3, particle size range is at 20 μ m-200 μ m, and composition and physical property are in table 1.
Embodiment 4
Mode according to embodiment 3 is prepared contact agent, different, and foramen magnum-mesoporous magnesia is by micropore oxygenChange magnesium and replace, obtain contact agent, be numbered A4, particle size range, at 20 μ m-200 μ m, forms and physicsCharacter is in table 1.
Comparative example 3
By levigate to kaolin (Suzhou carclazyte) and boehmite (Shandong Aluminum Plant's production), average grain diameter is1.0 μ m. Get 6kg kaolin, add 12kg deionized water, stir 30 minutes. Getting 1.5kg intends thinDiaspore, adds 2.25kg deionized water, stirs, and adds nitric acid to regulate pH value to 1.5. WillTwo kinds of slurries mix and blends 30 minutes, spray shaping, at 600 DEG C, roasting obtains sample for 60 minutes,Be numbered D3, grain particle size range is at 20 μ m-200 μ m, and composition and physical property are 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 conductivity factor (W/mK) | 31 | 27 | 30 | 30 | 33 | 25 | 20 |
| Specific 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 |
| (μ m) for average grain diameter | 66 | 65 | 66 | 65 | 67 | 65 | 66 |
Embodiment 5-8 and comparative example 4-6
Use the fixed fluidized bed experimental provision of heavy oil to carry out all the other character of heavy petroleum hydrocarbon in table 2) contact and splitChange experiment. Catalyst inventory is 300 grams, 500 DEG C of reaction temperatures, weight (hourly) space velocity (WHSV) 5h-1, agent oil qualityThan 7, gas phase time of staying 1s in contact cracker, the mass ratio of steam and heavy oil feedstock is 0.5:1, crackate distribution experimental 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/% | Saturated 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
As can be seen from Table 3, under identical reaction condition, contact agent provided by the invention compares contrast mediumD3 liquid is received (liquefied gas, gasoline, diesel oil and heavy oil fraction) and has been improved nearly 12 percentage points, coke yieldApproximately 10 percentage points have declined.
Embodiment 9
Be that 15.10 % by weight, metal are that 50 μ g/g, sulfur content are by the contact agent and the carbon residue that are numbered A1The petroleum hydrocarbon heavy oil of 1.12% (quality) comes in contact cracking reaction in contact cracking unitary reactor,The process conditions of contact cracking reaction are: 460 DEG C of cracking temperature, weight (hourly) space velocity (WHSV) 10h-1, agent oil quality ratio10, water oil quality is than 0.1, and the heating rate that feedstock oil is heated to reaction temperature is 150 DEG C/s, gas phaseThe time of staying is 0.8s. Generate can distillate in reactor, distillate in 0.5s, be cooled to 350 DEG CBelow. Gained spent agent is 1.4 % by weight containing the coke content of charcoal contact agent (spent agent).
In gained crackate, dry gas yied is 1.1%, and coke yield is 13.60%, and it is 84.91% that liquid is received.Green coke factor coke/carbon residue is 0.9.
Spent agent enters gasifier after stripping. In dense bed, gas line speed is 0.25m/s, temperature620 DEG C, pass into containing oxygen 12.3% (mole), steam 87.7% (mole) gas, gas stop1.5 seconds time. (CO+H in gasification gas2)/CO2Mol ratio be 1.23, gasification gas in (butt)(CO+H2) molar content reach nearly 54.5%, H2S accounts for 95.3% (volume) of total sulfur in gasification gas,COS accounts for 4.5% (volume) of total sulfur in gasification gas. Contact agent after regeneration returns in cracker.
Embodiment 10
Be that 18.10 % by weight, metal are 200 μ g/g, sulfur content by the contact agent and the carbon residue that are numbered A2The petroleum hydrocarbon heavy oil that is 1.12% (quality) comes in contact cracking reaction in contact cracking unitary reactor,The process conditions of contact cracking reaction are: 500 DEG C of cracking temperature, weight (hourly) space velocity (WHSV) 20h-1, agent oil quality is than 7,Water oil quality is than 0.2, and the heating rate that feedstock oil is heated to reaction temperature is 100 DEG C/s, and gas phase stopsTime is 1.0s. Generate can distillate in reactor, distillate in 0.5s, be cooled to below 350 DEG C.Gained spent agent is 2.4 % by weight containing the coke content of charcoal contact agent (spent agent).
In gained crackate, dry gas yied is 1.8%, and coke yield is 16.83%, and it is 81.37% that liquid is received.Green coke factor coke/carbon residue is 0.93.
Spent agent enters gasifier after stripping. In dense bed, gas line speed is 0.12m/s, temperature680 DEG C, pass into air, gas residence time 5 seconds. (CO+H in gasification gas2)/CO2Mol ratio be1.32, (butt) (CO+H in gasification gas2) molar content reach nearly 56.1%, H2S accounts in gasification gas93.4% (volume) of total sulfur, COS accounts for 4.3% (volume) of total sulfur in gasification gas. Connecing after regenerationTactile agent is returned in cracker.
Embodiment 11
Be that 35.0 % by weight, metal are that 425 μ g/g, sulfur content are by the contact agent and the carbon residue that are numbered A3The petroleum hydrocarbon heavy oil of 3.12% (quality) comes in contact cracking reaction in contact cracking unitary reactor,The process conditions of contact cracking reaction are: 520 DEG C of cracking temperature, weight (hourly) space velocity (WHSV) 50h-1, agent oil quality ratio20, water oil quality is than 0.5, and the heating rate that feedstock oil is heated to reaction temperature is 200 DEG C/s, gas phaseThe time of staying is 0.5s. Generate can distillate in reactor, distillate in 0.5s, be cooled to 350 DEG CBelow. Gained spent agent is 1.6 % by weight containing the coke content of charcoal contact agent (spent agent).
In gained crackate, dry gas yied is 1.2%, and coke yield is 31.85%, and it is 66.95% that liquid is received.Green coke factor coke/carbon residue is 0.91.
Spent agent enters gasifier after stripping. In dense bed, gas line speed is 0.40m/s, temperature560 DEG C, pass into containing oxygen 30% (mole), steam 40% (mole), carbon dioxide 30% (mole)Gas, gas residence time 50 seconds. (CO+H in gasification gas2)/CO2Mol ratio be 1.4, gasification(butt) (CO+H in gas2) molar content reach nearly 56.0%, H2S account for gasification gas in total sulfur 96.1%(volume), COS accounts for 3.8% (volume) of total sulfur in gasification gas. Contact agent after regeneration returns to crackingIn reactor.
Embodiment 12
Be that 15.10 % by weight, metal are that 50 μ g/g, sulfur content are by the contact agent and the carbon residue that are numbered A1The petroleum hydrocarbon heavy oil of 1.12% (quality) comes in contact cracking reaction in contact cracking unitary reactor,The process conditions of contact cracking reaction are: 468 DEG C of cracking temperature, weight (hourly) space velocity (WHSV) 9h-1, agent oil quality is than 12,Water oil quality is than 0.15, and the heating rate that feedstock oil is heated to reaction temperature is 120 DEG C/s, and gas phase stopsTime is 0.75s, and gross pressure (gauge pressure) is 0.5MPa, and hydrogen dividing potential drop is 0.1MPa, and hydrogen-oil ratio is 1000m3/m3. Generate can distillate in reactor, distillate in 0.5s, be cooled to below 350 DEG C. InstituteObtaining spent agent is 1.2 % by weight containing the coke content of charcoal contact agent (spent agent).
In gained crackate, dry gas yied is 1.12%, and coke yield is 13.89%, and it is 84.99% that liquid is received.
Green coke factor coke/carbon residue is 0.92.
Spent agent enters gasifier after stripping. In dense bed, gas line speed is 0.25m/s, temperature620 DEG C, pass into containing oxygen 12.3% (mole), steam 87.7% (mole) gas, gas stop1.5 seconds time. (CO+H in gasification gas2)/CO2Mol ratio be 1.32, H2S accounts for total sulfur in gasification gas95.7% (volume), COS accounts for 3.8% (volume) of total sulfur in gasification gas. Contact agent after regenerationReturn in cracker.
Embodiment 13
Be that 18.10 % by weight, metal are 250 μ g/g, sulfur content by the contact agent and the carbon residue that are numbered A2The petroleum hydrocarbon heavy oil that is 1.52% (quality) comes in contact cracking reaction in contact cracking unitary reactor,The process conditions of contact cracking reaction are: 488 DEG C of cracking temperature, weight (hourly) space velocity (WHSV) 18h-1, agent oil quality ratio10, water oil quality is than 0.35, and the heating rate that feedstock oil is heated to reaction temperature is 120 DEG C/s, gas phaseThe time of staying is 1.75s, and gross pressure (gauge pressure) is 0.8MPa, and hydrogen dividing potential drop is 0.3MPa, and hydrogen-oil ratio is200m3/m3. Generate can distillate in reactor, distillate in 0.5s, be cooled to below 350 DEG C.Gained spent agent is 1.7 % by weight containing the coke content of charcoal contact agent (spent agent).
In gained crackate, dry gas yied is 1.75%, and coke yield is 16.83%, and it is 81.42% that liquid is received.
Green coke factor coke/carbon residue is 0.93.
Spent agent enters gasifier after stripping. In dense bed, gas line speed is 0.20m/s, temperature680 DEG C, pass into containing oxygen 22.3% (mole), steam 77.7% (mole) gas, gas stop3 seconds time. (CO+H in gasification gas2)/CO2Mol ratio be 1.23, H2S accounts for total sulfur in gasification gas94.6% (volume), COS accounts for 3.9% (volume) of total sulfur in gasification gas. Contact agent after regeneration returnsReturn in cracker.
Embodiment 14
Be that 35.0 % by weight, metal are that 550 μ g/g, sulfur content are by the contact agent and the carbon residue that are numbered A3The petroleum hydrocarbon heavy oil of 3.25% (quality) comes in contact cracking reaction in contact cracking unitary reactor,The process conditions of contact cracking reaction are: 535 DEG C of cracking temperature, weight (hourly) space velocity (WHSV) 38h-1, agent oil quality ratio15, water oil quality is than 0.45, and the heating rate that feedstock oil is heated to reaction temperature is 120 DEG C/s, gas phaseThe time of staying is 1.75s, and gross pressure (gauge pressure) is 0.7MPa, and hydrogen dividing potential drop is 0.2MPa, and hydrogen-oil ratio is 400m3/m3. Generate can distillate in reactor, distillate in 0.5s, be cooled to below 350 DEG C.Gained spent agent is 5.3 % by weight containing the coke content of charcoal contact agent (spent agent).
In gained crackate, dry gas yied is 1.21%, and coke yield is 31.85%, and it is 66.94% that liquid is received.
Green coke factor coke/carbon residue is 0.91.
Spent agent enters gasifier after stripping. In dense bed, gas line speed is 0.20m/s, temperature680 DEG C, pass into containing oxygen 22.3% (mole), steam 77.7% (mole) gas, gas stop3 seconds time. (CO+H in gasification gas2)/CO2Mol ratio be 1.45, H2S accounts for total sulfur in gasification gas95.0% (volume), COS accounts for 4.1% (volume) of total sulfur in gasification gas. Contact agent after regeneration returnsReturn in cracker.
Comparative example 7
By active carbon (originating identical with embodiment 3) and carbon residue be 35.0 % by weight, metal be 550 μ g/g,Sulfur content is that the petroleum hydrocarbon heavy oil of 3.25% (quality) comes in contact and splits in contact cracking unitary reactorChange reaction, the process conditions of contact cracking reaction are: 535 DEG C of cracking temperature, weight (hourly) space velocity (WHSV) 38h-1, agentOil quality is than 15, and water oil quality is than 0.45, and the heating rate that feedstock oil is heated to reaction temperature is120 DEG C/s, the gas phase time of staying is 1.75s, and gross pressure (gauge pressure) is 0.7MPa, and hydrogen dividing potential drop is 0.2MPa,Hydrogen-oil ratio is 400m3/m3. Generate can distillate in reactor, distillate in 0.5s, be cooled toBelow 350 DEG C. Gained spent agent is 2.8 % by weight containing the coke content of charcoal contact agent (spent agent).
In gained crackate, dry gas yied is 2.1%, and coke yield is 42.0%, and it is 55.9% that liquid is received.
Green coke factor coke/carbon residue is 1.2.
Spent agent enters gasifier after stripping. In dense bed, gas line speed is 0.20m/s, temperature680 DEG C, pass into containing oxygen 22.3% (mole), steam 77.7% (mole) gas, gas stop3 seconds time. (CO+H in gasification gas2)/CO2Mol ratio be 1.35, H2S accounts for total sulfur in gasification gas94.7% (volume), COS accounts for 4.5% (volume) of total sulfur in gasification gas. Contact agent after regeneration returnsReturn in cracker.
Embodiment 14 can be found out compared with comparative example 7, and embodiment 14 is provided by the present invention by takingContact agent and using method, dry gas reduce 0.9 percentage point, coke reduce 10.2 percentage points, liquid receiveImprove 11.0 percentage points, (butt) (CO+H in gas gasifies simultaneously2) molar content reach 60%,Sulphur in gasification gas is mainly H2S, is conducive to the recovery of sulphur.
More than describe the preferred embodiment of the present invention in detail, still, the present invention is not limited to above-mentioned realityExecute the detail in mode, within the scope of technical conceive of the present invention, can be to technical side of the present inventionCase is carried out multiple simple variant, and these simple variant all belong to protection scope of the present invention.
It should be noted that in addition each the concrete technology spy described in above-mentioned detailed description of the inventionLevy, in reconcilable situation, can combine by any suitable mode. For fear of needn'tThe repetition of wanting, the present invention is to the explanation no longer separately of various possible combinations.
In addition, between various embodiment of the present invention, also can be combined, as long as itsWithout prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (16)
1. a contact agent, this contact agent is made up of aluminium oxide and magnesia.
2. contact agent according to claim 1, wherein, taking the total amount of described contact agent as benchmark,The content of aluminium oxide is 20-80 % by weight, and magnesian content is 20-80 % by weight.
3. contact agent according to claim 1 and 2, wherein, the thermal conductivity factor of described contact agentFor 20-50W/ (mK), be preferably 25-37W/ (mK).
4. according to the contact agent described in any one in claim 1-3, wherein, the ratio of this contact agentSurface area >=10m2/ g, pore volume is 0.05-1cm3/g。
5. according to the contact agent described in any one in claim 1-4, wherein, the ratio of this contact agentSurface area is 50-150m2/ g, pore volume is 0.05-0.4cm3/g。
6. according to the contact agent described in any one in claim 1-5, wherein, described contact agentProfile is microballoon shape, and average grain diameter is 50-75 μ m, and particle size range is 20-200 μ m.
7. according to the contact agent described in any one in claim 1-6, wherein, described magnesia isForamen magnum-mesoporous magnesia, the aperture of macropore is 50-100nm, mesoporous aperture is 15-50nm.
8. a processing method for heavy petroleum hydrocarbon, the method is included in faces under hydrogen or conditions of non-hydrogen,By heavy petroleum hydrocarbon with contact agent contacting transmission of heat by contact in cracker, heavy petroleum hydrocarbon is connectTouch cracking reaction, it is characterized in that, described contact agent is connecing described in any one in claim 1-7Touch agent.
9. processing method according to claim 8, wherein, under conditions of non-hydrogen, contact crackingThe condition of reaction comprises reaction temperature 450-650 DEG C, weight (hourly) space velocity (WHSV) 1-100h-1, contact agent and heavy oil feedstockMass ratio be 1-30:1, gas phase time of staying 0.5-2.0s in contact cracker, steam is with heavyThe mass ratio of oil raw material is 0.05-1:1;
Under hydro condition, the condition of contact cracking reaction comprises reaction temperature 450-650 DEG C, weighs space-timeSpeed 1-100h-1, the mass ratio of contact agent and heavy oil feedstock is 1-30:1, the matter of steam and heavy oil feedstockAmount is than being 0.05-1:1, and gross pressure is 0-1MPa, and hydrogen dividing potential drop is 0.1-0.5MPa, and hydrogen-oil ratio is10-1500m3/m3, in contact cracker, the gas phase time of staying is 0.5-4.0s.
10. processing method according to claim 9, wherein, described heavy petroleum hydrocarbon is heated toThe heating rate of reaction temperature is 20-500 DEG C/s.
11. processing methods according to claim 8, wherein, the carbon residue of described heavy petroleum hydrocarbonFor 10-45 % by weight, tenor is 25-1000 μ g/g.
12. processing methods according to claim 8, wherein, the method also comprises contact crackingWhat reaction generated can distillate distillate in reactor, in 0.5s, be cooled to below 350 DEG C.
13. processing methods according to claim 12, wherein, the method also comprises and will deposit JiaoThe contact agent to be generated of charcoal is sent in fluidized-bed gasifier, under the gasifying agent that contains oxygen exists, makes contactCharcoal in agent reacts with gasifying agent, and contact agent and be rich in CO, H obtains regenerating2Gasification gas, fluid bedIn gasifier, reaction condition comprises that gas residence time is 0.5-60 second, and the gasification temperature of dense bed is550-1000 DEG C, the linear velocity of dense bed is 0.05-0.6m/s; Preferably, gas residence time is 1.0-10Second, the gasification temperature of dense bed is 600-950 DEG C, the linear velocity of dense bed is 0.2-0.6m/s.
14. methods according to claim 13, wherein, in gasifying agent, oxygen mole fraction is5%-30%, is preferably 5%-20%, and all the other are nitrogen or steam or carbon dioxide, or in them two kindsOr two or more mixture.
15. methods according to claim 13, wherein, the sulphur in gasification gas is mainly with H2S and COSForm exist, H in the gas that preferably gasifies2More than S and COS account for 99.0 volume % of total sulfur in gasification gas.
16. processing methods according to claim 13, wherein, the method also comprises gained is gasifiedPneumatic transmission enters sulfur recovery unit and removes sulphur, and the gasification gas after gained desulfurization, after Water gas shift/WGS device, separatesObtain hydrogen and CO2Or as fuel gas application, or be used for generating or as boiler oil after desulfurizationThere is steam.
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| 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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| 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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