CN105567308A - Method for reducing calcium content in atmospheric pressure residual oil and method for processing atmospheric pressure residual oil - Google Patents
Method for reducing calcium content in atmospheric pressure residual oil and method for processing atmospheric pressure residual oil Download PDFInfo
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Abstract
The present invention discloses a method for reducing calcium content in atmospheric pressure residual oil, the method comprises the following steps: first, using a solvent for deasphalting processing of the atmospheric pressure residual oil to obtain deasphalted oil, wherein the content of n-heptane-insoluble matters in the obtained deasphalted oil is not more than 0.3% by weight by controlling of conditions of the solvent deasphalting processing; and then under aqueous solution conditions, contacting a demulsifier and a decalcifying agent with the obtained deasphalted oil for oil-water separation. The present invention also discloses a method for processing the atmospheric pressure residual oil, and the method comprises contacting of an oil phase material obtained by the method for reducing the calcium content in the atmospheric pressure residual oil with a hydrogenation catalyst. According to the method, under the premise of using of a relatively small amount of the decalcifying agent, the calcium content in high calcium content atmospheric pressure residual oil can be efficiently and cost-effectively reduced.
Description
Technical field
The present invention relates to and a kind ofly reduce the method for calcium contents in long residuum and a kind of processing and treating method of long residuum.
Background technology
Along with petroleum resources are increasingly valuable, the efficiency utilization of heavy oil is more and more subject to people's attention, and residual hydrogenation process is a kind of high liquid product yield technique, obtains increasingly extensive application.According to the type of reactor, residual hydrogenation process can be divided into fixed-bed process, boiling bed process, suspension bed (also known as slurry bed system) technique and moving bed process, wherein fixed bed residual hydrocracking technical matters is ripe, simple to operate, is most widely used.
Such as, but fixed bed residual hydrocracking technique also has its limitation, and catalyzer can not be changed online.And, also there is certain restriction to the raw material oil properties that it is processed, such as, because asphaltene molecules amount is comparatively large, be difficult to carry out hydrocracking and dehydrogenative condensation reaction easily occurs, and then causing catalyst carbon deposit inactivation; And be also enriched metallic nickels a large amount of in residual oil and vanadium etc. in bituminous matter, nickel and vanadium can generate metallic sulfide covering catalyst metal active centres after hydrotreatment, cause catalyst deactivation.
Therefore to its process stock oil character also have certain restriction.Wherein, in raw material, the content of calcium is an important Con trolling index (general requirement controls lower than 10 μ g/g).Hydrogenation and removing reaction is there is in the calcium containing compound in feed residue in fixed bed residual oil reactor, be deposited between the nearly surface of catalyzer, outside surface and particle with the form of sulfurated lime, catalyst deactivation and bed is caused to harden, bed pressure drop is caused to raise, device can be made time serious to be forced to stop work, and therefore the calcium contents of fixed bed Residue Hydrotreating Technology to raw material has stricter restriction.
But calcium contents height is one of feature of crude oil in China, the calcium in crude oil is enriched in residual oil, and mainly concentrates in the resin and asphalt of residual oil.Therefore, the refinery with fixed bed residual hydrogenation equipment, when processing High calcium containing crudes, needs before crude oil enters atmospheric and vacuum distillation unit, use a large amount of decalcifying agents to carry out decalcification process.But a large amount of uses of the additives such as decalcifying agent cause cost to increase, and find in some refinery, use the calcium contents after a large amount of decalcifying agent in residual oil still higher, even if continue the injection rate strengthening decalcifying agent, the calcium content decreased in residual oil is not remarkable.
At present, need badly in this area find a kind of newly can low cost and reduce the method with calcium contents in the long residuum of high calcium content expeditiously.
Summary of the invention
The object of the invention is the defect overcoming prior art, just can high-level efficiency and reduction at low cost has the method for calcium contents in the long residuum of high calcium content under the prerequisite of decalcifying agent using small amount, and utilize the method for calcium contents in above-mentioned reduction long residuum to provide a kind of processing and treating method with the long residuum of high calcium content.
The present inventor finds based on after large quantifier elimination: the calcium in residual oil is mainly distributed in resin and asphalt.Use decalcifying agent to be easier to the calcium in colloid to remove, but calcium in bituminous matter is more difficult removes.Even when therefore adopting the method for prior art to add a large amount of decalcifying agents in the crude oil with high calcium content, the calcium be distributed in bituminous matter also usually can not be made to remove, heavy dose of like this decalcifying agent that uses also can make tooling cost increase substantially.And bituminous matter occurs when fixed bed residual hydrocracking to transform or deposition process, bitum calcium and then be deposited on residual oil hydrocatalyst bed, cause hydrogenation catalyst bed laminate tie and cause bed pressure drop to raise, affect catalyzer work-ing life.Because bituminous matter can not occur to transform or deposition process in the protective material that activity is lower; calcium in bituminous matter can not be deposited in protective material; even therefore add conventional protective material when wanting the impurity such as calcium, iron removed in hydrotreated feed in hydroprocessing processes, also above-mentioned defect can not be avoided.
In view of characteristic distributions and the shedding law of above-mentioned calcium ion, the present inventor expects after atmospheric and vacuum distillation step based on above-mentioned thinking, in technological process before residual hydrocracking step, Calcium treatment step falls in design, thus can under the condition of the least possible use decalcifying agent, effectively reduce the calcium contents of residual oil, the catalyzer shortening in work-ing life can effectively avoiding the catalyzer in hydroprocessing processes to cause due to the deposition of sulfurated lime, and residual oil after diasphaltene is comparatively slow at hydroprocessing processes catalyst deactivation, can extending catalyst life cycle, therefore method of the present invention can reduce production cost from overall flow.
To achieve these goals, on the one hand, the invention provides a kind of method reducing calcium contents in long residuum, the method comprises:
(1) long residuum is carried out solvent deasphalting process, obtain deasphalted oil, wherein, the condition controlling solvent deasphalting process makes N.heptane insolubles content in deasphalted oil not higher than 0.3 % by weight;
(2) under aqueous conditions, the deasphalted oil that decalcifying agent and emulsion splitter and step (1) obtain is contacted and carries out oily water separation.
On the other hand, the invention provides a kind of processing and treating method of long residuum, the method comprises:
(1) long residuum is carried out solvent deasphalting process, obtain deasphalted oil, wherein, the condition controlling solvent deasphalting process makes N.heptane insolubles content in deasphalted oil not higher than 0.3 % by weight;
(2) under aqueous conditions, the deasphalted oil that decalcifying agent and emulsion splitter and step (1) obtain is contacted and carries out oily water separation;
(3) in presence of hydrogen, the material containing the oil phase obtained after step (2) is contacted with hydrogenation catalyst.
By adopting the method for calcium contents and the processing and treating method of long residuum in above-mentioned reduction long residuum provided by the invention, also namely first long residuum is carried out solvent deasphalting process to the N.heptane insolubles content in the deasphalted oil obtained not higher than 0.3 % by weight, and then when using decalcifying agent to carry out the method for decalcification process, just the calcium contents had in the long residuum of high calcium content can be reduced expeditiously under the prerequisite of decalcifying agent using small amount, and aforesaid method of the present invention has advantage simple to operate, with low cost.Particularly, such as can be seen from the result of embodiments of the invention 1 and comparative example 1 just, when there is the long residuum of high calcium content (calcium contents in such as embodiment 1 is 45 μ g/g) by adopting method of the present invention processing, only need to use a small amount of decalcifying agent that the calcium contents in decalcification DAO just can be made to be down to extremely low level; And during the long residuum adopting the method process of comparative example 1 identical, even use the decalcifying agent of a large amount of identical type that the calcium contents in decalcification DAO also only can be made to be down to common level, and beds average reaction temperature is higher when reaching like products quality, running period is short.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
On the one hand, the invention provides a kind of method reducing calcium contents in long residuum, the method comprises:
(1) long residuum is carried out solvent deasphalting process, obtain deasphalted oil (DAO), wherein, the condition controlling solvent deasphalting process makes N.heptane insolubles content in deasphalted oil not higher than 0.3 % by weight;
(2) under aqueous conditions, the deasphalted oil that decalcifying agent and emulsion splitter and step (1) obtain is contacted and carries out oily water separation.
In reduction long residuum of the present invention calcium contents method in, in step (1), the condition preferably controlling solvent deasphalting process makes N.heptane insolubles content in deasphalted oil not higher than 0.1 % by weight.
In method of the present invention, can the DAO obtained in step (1) be directly used in step (2), also can before DAO being used for step (2), adopt this area ordinary method to carry out conventional processing, to this, there is no particular limitation in the present invention.
In the method for the invention, the method of preferred described solvent deasphalting process can be: described long residuum and solvent are entered from the upper and lower of extraction tower respectively, in extraction tower, carrying out counter current contact, also can being first separated by entering extraction tower after pre-mixing again.Solvent deasphalting both can carry out extracting under the undercritical conditions of solvent, also can carry out extracting under the super critical condition of solvent.Specific operation process and the solvent recovery process of solvent deasphalting process are well known to the skilled person, and the present invention does not repeat them here.
In the method for the invention, can also obtain de-oiled asphalt after described solvent deasphalting process, described de-oiled asphalt can be used as the purposes such as gasified raw material, boiler oil, pitch mediation raw material.
In reduction long residuum of the present invention calcium contents method in, in step (1), the condition of preferred control solvent deasphalting process makes described deasphalted oil be more than 70% relative to the yield of described long residuum, be more preferably more than 80%, be particularly preferably more than 90%.
In reduction long residuum of the present invention calcium contents method in, in step (1), in described long residuum, can for being not less than 10 μ g/g in the calcium contents of calcium ion; Preferably be not less than 20 μ g/g.
In reduction long residuum of the present invention calcium contents method in, in step (1), the initial boiling point of preferred described long residuum is 350-400 DEG C.
In reduction long residuum of the present invention calcium contents method in, in step (1), the density of preferred described long residuum is not higher than 1.0g/mL.
In reduction long residuum of the present invention calcium contents method in, in step (1), the solvent in described solvent deasphalting process can for being selected from least one in the alkane of C5-C8, the alkene of C5-C8, condensate oil and petroleum naphtha; Preferably be selected from least one in the alkane of C5-C8; Be more preferably at least one be selected from the alkane of C7, such as normal heptane etc.
In method of the present invention, it is any one straight or branched alkane in 5,6,7 or 8 that the alkane of described C5-C8 comprises carbonatoms, and the present invention is preferably the straight-chain paraffin of C5-C8.It is any one straight or branched alkene in 5,6,7 or 8 that the alkene of described C5-C8 comprises carbonatoms, and the present invention is preferably the normal olefine of C5-C8.The alkane of described C7 comprises the straight or branched alkane that carbonatoms is 7.
According to the method for calcium contents in reduction long residuum of the present invention, wherein, in step (1), the condition of described solvent deasphalting process can comprise: temperature is 60-280 DEG C; Be preferably 100-240 DEG C.
According to the method for calcium contents in reduction long residuum of the present invention, wherein, in step (1), the condition of described solvent deasphalting process can comprise: pressure is 1-6MPa; Be preferably 3-5MPa.
According to the method for calcium contents in reduction long residuum of the present invention, wherein, in step (1), the condition of described solvent deasphalting process can comprise: the input material volume ratio of solvent and long residuum is 0.5-30:1; Be preferably 3-15:1.
In reduction long residuum of the present invention calcium contents method in, in step (2), relative to the calcium ion of ppm every in deasphalted oil, the consumption of described decalcifying agent can be 1-15ppm; Preferable amount is 3-10ppm.Such as, in the present invention, when the calcium ion concn in described deasphalted oil is 1 μ g/g, with the total amount of described deasphalted oil for benchmark, the consumption of described decalcifying agent can be 1-15 μ g/g.In the present invention, ppm refers to ppm by weight.
In reduction long residuum of the present invention calcium contents method in, in step (2), relative to every kg deasphalted oil, the consumption of described emulsion splitter is 1-1000mg.
In reduction long residuum of the present invention calcium contents method in, in step (2), relative to every kg deasphalted oil, the consumption of described water is 30-500g; Be preferably 50-200g.
According to a kind of concrete embodiment of the present invention, in reduction long residuum of the present invention calcium contents method in, in step (2), the consumption of described decalcifying agent, emulsion splitter and water can for the calcium contents in the oil phase that obtains after making to carry out oily water separation be higher than 5 μ g/g; More preferably no higher than 2 μ g/g.
According to the method for calcium contents in reduction long residuum of the present invention, in step (2), described decalcifying agent can be carbonate aqueous solution, the sulphonic acids aqueous solution, the phosphoric acid class aqueous solution, the carboxylic-acid aqueous solution and they are with the mixture of arbitrary proportion.But the present invention is to the kind of institute's decalcifying agent, and there is no particular limitation, can be the conventional various decalcifying agents used in this area, under preferable case, in order to advantageously in heavy oil decalcification process of the present invention, be preferably the JCM-2004RPD series decalcifying agent of Sinopec Research Institute of Petro-Chemical Engineering research and development.
According to the method for calcium contents in reduction long residuum of the present invention, in step (2), described emulsion splitter can be alkyl phenolic resin polyoxyethylene poly-oxygen propylene aether, polysiloxane polyoxyethylene polyethenoxy ether, poly phosphate, polyoxyethylene poly-oxygen propylene aether, the vulcabond modifier of polyoxyethylene oxypropylene (or butylene) ether, high carbon number alkyl imidazoline, oxygen ethylization fatty alcohol ether sulphate and they are with the mixture of arbitrary proportion.But the present invention is to the kind of institute's emulsion splitter, and there is no particular limitation, can be the conventional various emulsion splitters used in this area, under preferable case, in order to advantageously in heavy oil decalcification process of the present invention, be preferably the JC-2004RP series emulsion splitter of Sinopec Research Institute of Petro-Chemical Engineering research and development.
In reduction long residuum of the present invention calcium contents method in, in step (2), in the present invention, it should be noted that, described aqueous conditions can be formed by using water (comprising deionized water and/or distilled water), and the consumption of water is for meeting aforementioned proportion, in the water preferably used, calcium and Mg content sum are lower than 10 μ g/g.
In the present invention, the content of the solid particulate matter in the oil phase obtained after preferred oily water separation is not higher than 10 μ g/g.
According to the method for calcium contents in reduction long residuum of the present invention, wherein, in step (2), to the density of described deasphalted oil, there is no particular limitation, under preferable case, in order to more be of value to follow-up oily water separation step and make the reduction calcium contents effect of method of the present invention better, the density of the deasphalted oil used in preferred steps (2) is below 0.95g/mL, is preferably below 0.945g/mL.According to method of the present invention, it should be noted that, when the density of the deasphalted oil obtained after step (1) is not in above-mentioned scope, those skilled in the art can adopt the conventional various methods used to dilute etc. obtained deasphalted oil, make the density for the deasphalted oil in step (2) be below 0.95g/mL, be preferably below 0.945g/mL.
According to the method for calcium contents in reduction long residuum of the present invention, wherein, in step (2), the temperature of described oily water separation is can 50-200 DEG C.
In method of the present invention, to the method for described oily water separation, there is no particular limitation, and the various methods that those skilled in the art can use according to routine carry out oily water separation.Under preferable case, in the method for the invention, in order to fast and effeciently be separated, and the calcium contents in the oil phase obtained after effectively reducing oily water separation, the mode of oily water separation of the present invention comprises hot standing separation and/or conventional electric desalting process.Under electric field action, velocity of separation is faster, general suitable electric-force gradient be 100-2000 volt/centimetre; The time be separated completely separately is as the criterion with profit.Specific operation process is well known to the skilled person, and does not repeat them here.
On the other hand, the invention provides a kind of processing and treating method of long residuum, the method comprises:
(1) long residuum is carried out solvent deasphalting process, obtain deasphalted oil, wherein, the condition controlling solvent deasphalting process makes N.heptane insolubles content in deasphalted oil not higher than 0.3 % by weight;
(2) under aqueous conditions, the deasphalted oil that decalcifying agent and emulsion splitter and step (1) obtain is contacted and carries out oily water separation;
(3) in presence of hydrogen, the material containing the oil phase obtained after step (2) is contacted with hydrogenation catalyst.
It should be noted that, in the processing and treating method of a kind of long residuum provided by the invention, described step (1) and step (2) can adopt any one or the various ways described in the method about reducing calcium contents in long residuum of the present invention to carry out, involved operating parameters and raw material type etc. are all identical with the method for calcium contents in above-mentioned reduction long residuum, and the processing and treating method of long residuum of the present invention does not repeat them here.
In the present invention, the described oil phase obtained after step (2) is also referred to as decalcification DAO.
In the method for the invention, described decalcification DAO can separately as the raw material of fixed bed hydrogenation treating processes, also can hydrocarbon ils (such as with other conventional low ca contents (lower than 10 μ g/g), long residuum, decompressed wax oil, vacuum residuum, wax tailings, catalytic cracking circulation wet goods) use as the raw material of fixed bed hydrogenation treating processes after mixing, to this, there is no particular limitation in the present invention.
In the present invention, preferred described decalcification DAO or described decalcification DAO enters fixed bed hydrotreating reactors after mixing with other conventional low ca content hydrocarbon ils and hydrogen, contacts with the hydrogenation catalyst loaded in reactor.
The condition that the preferred described oil phase of the present invention contacts with hydrogenation catalyst comprises: beds average reaction temperature is 300-425 DEG C, hydrogen dividing potential drop is 5.0-18.0MPa, mark that state hydrogen to oil volume ratio is 100-1500:1, volume space velocity is 0.1-1.0h
-1.
In method of the present invention, by the product liquid that obtains after hydrotreatment after distillation process, dry gas, liquefied gas, hydrotreated naphtha, hydrogenated diesel oil and hydrogenated residue can be obtained respectively; Wherein hydrogenated residue is primary product, yield usually more than 85%, generally as catalytically cracked material.
In the present invention, in step (3), ordinary method can be adopted in oil phase and hydrogenation catalyst contact process to detect sulphur content in hydrogenated residue, if sulphur content is more than 0.4 % by weight in hydrogenated residue, then suitably can improve the average reaction temperature of beds, controlling sulphur content in hydrogenated residue is 0.35-0.4 % by weight.When fixed-bed reactor continuous service makes single reactor average reaction temperature reach 410 DEG C, or when single reactor pressure decrease reaches 0.5MPa, be namely judged as reaching maximum average temperature that reactor allows or maximal pressure falls, carry out shutdown process.That is, when reaching one of above-mentioned two kinds of conditions, being namely judged as reaching maximum average temperature that reactor allows or maximal pressure falls, carrying out shutdown process.
In method of the present invention, preferred described hydrogenation catalyst comprises at least two kinds of catalyzer and adopts series connection grading loading.According to the present invention, according to the flow direction of described stock oil, in described hydrotreating reactor, be disposed with hydrogenation protecting catalyst bed, Hydrodemetalation catalyst bed and Hydrobon catalyst bed.Described Hydrobon catalyst bed can comprise at least one in Hydrobon catalyst bed, removal of ccr by hydrotreating beds and hydrodenitrogenation catalyst bed.Described hydrotreating catalyst can be arranged in the fixed bed hydrogenation reactor of one or more series connection.Wherein, the filling ratio of the number that all kinds of beds is arranged and all kinds of catalyzer can be the routine selection of this area, and to this, there is no particular limitation in the present invention.
In the present invention, used catalyzer such as hydrogenation protecting catalyst, Hydrodemetalation catalyst, Hydrobon catalyst, removal of ccr by hydrotreating catalyzer, hydrodenitrogenation catalyst can be all the hydrogenation catalyst with these functions of this area routine.Usually, above-mentioned catalyzer be all with porous inorganic oxide as aluminum oxide be carrier, with group VIB and/or group VIII metal as the oxide compound of one or more in W, Mo, Co and Ni is active ingredient, optionally adds other various auxiliary agent as one or more catalyzer in P, Si, F and B.Combinationally use after can being purchased separately various catalyzer during use; also the complete series catalyst for hydrotreatment of residual oil comprising above-mentioned various catalyzer can be directly purchased, as RG, RDM, RMS and RSC series hydrotreating guard catalyst for residual oil, Hydrodemetalation catalyst, Hydrobon catalyst and removal of ccr by hydrotreating catalyzer purchased from Sinopec catalyzer Chang Ling branch office.Such as; in an embodiment of the present invention, RG-30B hydrogenation protecting catalyst, RDM-32 Hydrodemetalation catalyst, RDM-33 hydrodemetallation (HDM) desulfurization catalyst, RMS-30 Hydrobon catalyst and RCS-30 carbon residue hydrogenation conversion catalyst is exemplarily adopted to load described fixed-bed reactor successively.
The preferred embodiment of one according to the present invention, the invention provides a kind of processing and treating method of long residuum, specifically comprises:
(1) long residuum solvent deasphalting process: long residuum and low molecular hydrocarbon kind solvent, through solvent deasphalting process extracting, obtain deasphalted oil (DAO) and de-oiled asphalt respectively;
(2) DAO decalcification treating processes: carry out oil phase and aqueous phase separation after being mixed with decalcifying agent, emulsion splitter and water by DAO, obtains calcic sewage and decalcification DAO respectively;
(3) decalcification DAO fixed bed hydrogenation treating processes: decalcification DAO (separately or mix other common residual hydrogenation raw material) hydrogenation enters fixed bed residual hydrogenation equipment, reacts under hydrogen and catalyzer existent condition.
In above-mentioned reduction long residuum provided by the invention, the advantage of the method for calcium contents and the processing and treating method of long residuum is mainly:
(1) method provided by the invention is adopted can to realize with fixed bed hydrogenation treatment process, to process the long residuum of high calcium content, having expanded the stock oil adaptability of fixed bed residual hydrocracking device;
(2) usage quantity of the additives such as decalcifying agent is considerably reduced, cost-saving;
(3) after diasphaltene and decalcifying agent process, the stock oil character entering fixed bed residual hydrogenation equipment is significantly improved, density reduces, bituminous matter almost all removes, calcium and the metal content such as nickel and vanadium significantly reduce, can reduce in fixed bed residual oil hydrocatalyst grading distribution scheme low activity, wide-aperture Hydrodemetalation catalyst filling ratio, increase the filling ratio of high activity hydrogenation and desulphurization, de-carbon residue catalyzer, improve residual hydrogenation product characteristics, extend the operational cycle of fixed bed residual hydrocracking device.
Below will be described the present invention by embodiment.In following examples and comparative example, decalcifying agent used is the JCM-2004RPD decalcifying agent of Sinopec Research Institute of Petro-Chemical Engineering research and development; Emulsion splitter is the JC-2004RP emulsion splitter of Sinopec Research Institute of Petro-Chemical Engineering research and development; Various hydrotreating catalyst is the RHT series residual oil hydrocatalyst that Sinopec catalyzer branch office produces.
Embodiment 1
The present embodiment is for illustration of the method for calcium contents and the processing and treating method of long residuum in reduction long residuum of the present invention.
High calcium content long residuum character sees the following form 1.
(1) carry out solvent deasphalting process to high calcium content long residuum: normal heptane selected by solvent, extraction temperature 230 DEG C, working pressure 3MPa, solvent and atmospheric resid feed volume ratio are 8:1.After extracting, DAO is that in 93.3 % by weight, DAO, N.heptane insolubles content is 0.2 % by weight relative to the yield of long residue feed, and density is 0.945g/mL, and calcium contents is 26 μ g/g, and nickel content is 24.1 μ g/g, and content of vanadium is 9.8 μ g/g.
(2) decalcification process is carried out to DAO: decalcifying agent consumption is 150 μ g/g; Relative to the DAO of every kg, the add-on of described emulsion splitter is 50mg, and the consumption of described water is 100g; The DAO that decalcifying agent, emulsion splitter, water obtain with step (1) is fully mixed, under 90 DEG C, 250 volts of/centimetre of electric fields, acts on 4h, be then separated decalcification DAO (oil phase) and water (aqueous phase).Analyzing calcium contents in decalcification DAO is 1.9 μ g/g.
(3) bed hydroprocessing process is fixed to decalcification DAO: in fixed-bed reactor, load RG-30B hydrogenation protecting catalyst 50mL, RDM-32 Hydrodemetalation catalyst 150mL, RDM-33 hydrodemetallation (HDM) desulfurization catalyst 100mL, RMS-30 Hydrobon catalyst 300mL, RCS-30 carbon residue hydrogenation conversion catalyst 400mL successively along logistics direction, adds up to 1000mL.Hydroprocessing condition is: hydrogen dividing potential drop 14.0MPa, mark state hydrogen to oil volume ratio 500:1, volume space velocity 0.25h
-1, when operating initial, beds average reaction temperature is 360 DEG C; Detect sulphur content in hydrogenated residue, if sulphur content is more than 0.4 % by weight in hydrogenated residue, then suitably improve beds average reaction temperature, in control hydrogenated residue, sulphur content is at 0.35-0.4 % by weight.After running 8300h, average reactor temperature is 410 DEG C, and reactor pressure decrease is 0.5MPa, reaches maximum average temperature and the pressure drop of reactor permission simultaneously, stops work.
Table 1
| 20 DEG C of density (kg/m 3) | 965.5 |
| 100 DEG C of viscosity (mm 2/s) | 186.4 |
| S content (% by weight) | 1.6 |
| N content (μ g/g) | 4600 |
| Carbon residue (% by weight) | 11.7 |
| Ni content (μ g/g) | 69.4 |
| V content (μ g/g) | 32 |
| Ca content (μ g/g) | 45 |
| Initial boiling point (DEG C) | 350 |
Comparative example 1
The high calcium content long residuum as stock oil selected in this comparative example is in the same manner as in Example 1.
(1) directly carry out decalcification process to high calcium content long residuum: the consumption of decalcifying agent is 300 μ g/g, relative to the high calcium content long residuum of every kg, the add-on of described emulsion splitter is 100mg, and the consumption of described water is 100g; Decalcifying agent, emulsion splitter, water are fully mixed with high calcium content long residuum, under 90 DEG C, 250 volts of/centimetre of electric fields, act on 4h, be then separated after decalcification oil phase and aqueous phase.Analyzing calcium contents in the oil phase after decalcification is 12.1 μ g/g.
(2) bed hydroprocessing process is fixed to the oil phase after decalcification: in fixed-bed reactor, the kind of loading catalyst, loadings and type of feed are identical with embodiment 1.Hydroprocessing condition is identical with embodiment 1, and when operating initial, beds average reaction temperature is 360 DEG C; Detect sulphur content in hydrogenated residue, if sulphur content is more than 0.4 % by weight in hydrogenated residue, then suitably improve beds average reaction temperature, in control hydrogenated residue, sulphur content is at 0.35-0.4 % by weight.After running 6400h, beds average reaction temperature is 405 DEG C, and total reactor pressure reduces to 0.5MPa, and the maximal pressure reaching reactor permission falls, and stops work.
Can be found out by the result of comparing embodiment 1 and comparative example 1, diasphaltene process do not carried out to above-mentioned high calcium content long residuum in comparative example 1 and directly carry out decalcification process.Under this operational circumstances, although decalcifying agent and emulsion splitter usage quantity increase substantially, effectively can not reduce the calcium contents in oil phase; And without diasphaltene process, the density of raw material is higher, oil water separation process difficulty in decalcification treating processes; In hydroprocessing processes, in the stock oil of diasphaltene process, metal content, sulphur content, nitrogen content are all higher, and when reaching like products quality, catalyst bed reaction device pressure drop rise is very fast, and running period is short.
Comparative example 2
The high calcium content long residuum as stock oil that this comparative example is selected is in the same manner as in Example 1.
(1) carry out solvent deasphalting process to high calcium content long residuum: operational condition is identical with embodiment 1, the DAO character obtained is identical with embodiment 1.
(1) bed hydroprocessing process is directly fixed to the DAO undecalcified that step (1) obtains: in fixed-bed reactor, the kind of loading catalyst, loadings and type of feed are identical with embodiment 1.Hydroprocessing condition is identical with embodiment 1, and when operating initial, beds average reaction temperature is 360 DEG C; Detect sulphur content in hydrogenated residue, if sulphur content is more than 0.4 % by weight in hydrogenated residue, then suitably improve beds average reaction temperature, in control hydrogenated residue, sulphur content is at 0.35-0.4 % by weight.After running 5700h, beds average reaction temperature is 403 DEG C, and total reactor pressure reduces to 0.5MPa, and the maximal pressure reaching reactor permission falls, and stops work.
Can be found out by the result of comparing embodiment 1 and comparative example 2, comparative example 2 is carried out diasphaltene process to above-mentioned high calcium content long residuum, do not carry out decalcification process and is directly fixed bed hydroprocessing process.Under this operational circumstances, in DAO, calcium contents is higher, enters in fixed bed residual hydrogenation reactor, and hydrogenation decalcification reaction easily occurs, and the sulfurated lime of generation is deposited on beds to be caused the too fast rising of reactor pressure decrease and stops work.Beds average reaction temperature is higher, and running period is short.
Comparative example 3
The high calcium content long residuum as stock oil that this comparative example is selected is in the same manner as in Example 1.
(1) carry out solvent deasphalting process to high calcium content long residuum: normal heptane selected by solvent, extraction temperature 220 DEG C, working pressure 3MPa, solvent and atmospheric resid feed volume ratio are 6:1.After extracting, DAO is that in 95.3 % by weight, DAO, N.heptane insolubles content is 0.5 % by weight relative to the yield of long residue feed, and density is 0.948g/mL, and calcium contents is 30 μ g/g, and nickel content is 26.1 μ g/g, and content of vanadium is 11.2 μ g/g.
(2) decalcification process is carried out to DAO: decalcifying agent consumption is 250 μ g/g; Relative to the DAO of every kg, the add-on of described emulsion splitter is 80mg, and the consumption of described water is 100g; The DAO that decalcifying agent, emulsion splitter, water obtain with step (1) is fully mixed, under 90 DEG C, 250 volts of/centimetre of electric fields, acts on 4h, be then separated decalcification DAO (oil phase) and water (aqueous phase).Analyzing calcium contents in decalcification DAO is 4.8 μ g/g.
(3) bed hydroprocessing process is fixed to decalcification DAO: in fixed-bed reactor, the kind of loading catalyst, loadings and type of feed are identical with embodiment 1.Hydroprocessing condition is identical with embodiment 1, and when operating initial, beds average reaction temperature is 360 DEG C; Detect sulphur content in hydrogenated residue, if sulphur content is more than 0.4 % by weight in hydrogenated residue, then suitably improve beds average reaction temperature, in control hydrogenated residue, sulphur content is at 0.35-0.4 % by weight.After running 7200h, average reactor temperature is 408 DEG C, and reactor pressure decrease is 0.5MPa, and the maximal pressure reaching reactor permission falls, and stops work.
Can be found out by the result of comparing embodiment 1 and comparative example 3, after comparative example 3 pairs of steps (1) adjust, in DAO, N.heptane insolubles content is higher than the numerical value in embodiment 1, and calcium contents, nickel content and content of vanadium are also all higher than the numerical value in embodiment 1.In this case, in the decalcification process of step (2), even if increase the usage quantity of decalcifying agent, but decalcification effect is not as the situation of embodiment 1, and in the hydroprocessing processes of step (3), beds average reaction temperature and pressure drop, all higher than embodiment 1, are shorter than embodiment 1 running period.
Embodiment 2
The present embodiment is for illustration of the method for calcium contents and the processing and treating method of long residuum in reduction long residuum of the present invention.
The high calcium content long residuum as stock oil that the present embodiment is selected is in the same manner as in Example 1.
(1) carry out solvent deasphalting process to high calcium content long residuum: normal heptane selected by solvent, extraction temperature 240 DEG C, working pressure 5MPa, solvent and atmospheric resid feed volume ratio are 10:1.After extracting, DAO is that in 89.5 % by weight, DAO, N.heptane insolubles content is 0.08 % by weight relative to the yield of long residue feed, and density is 0.937g/mL, and calcium contents is 21.0 μ g/g, and nickel content is 22.1 μ g/g, and content of vanadium is 6.8 μ g/g.
(2) decalcification process is carried out to DAO: decalcifying agent consumption is 150 μ g/g; Relative to the DAO of every kg, the add-on of described emulsion splitter is 50mg, and the consumption of described water is 100g; The DAO that decalcifying agent, emulsion splitter, water obtain with step (1) is fully mixed, under 90 DEG C, 250 volts of/centimetre of electric fields, acts on 4h, be then separated decalcification DAO (oil phase) and water (aqueous phase).Analyzing calcium contents in decalcification DAO is 0.9 μ g/g.
(3) bed hydroprocessing process is fixed to decalcification DAO: in fixed-bed reactor, the kind of loading catalyst, loadings and type of feed are identical with embodiment 1.Hydroprocessing condition is identical with embodiment 1, and when operating initial, beds average reaction temperature is 360 DEG C; Detect sulphur content in hydrogenated residue, if sulphur content is more than 0.4 % by weight in hydrogenated residue, then suitably improve beds average reaction temperature, in control hydrogenated residue, sulphur content is at 0.35-0.4 % by weight.After running 8800h, beds average reaction temperature is 410 DEG C, and total reactor pressure reduces to 0.50MPa, and the maximal pressure reaching reactor permission falls, and stops work.
As can be seen from the result of the present embodiment, when adopting the method process long residuum of the present embodiment, by the condition of adjustment solvent deasphalting process to make in DAO N.heptane insolubles content lower than 0.1 % by weight time, calcium contents in decalcification DAO can be made significantly to reduce, and the cycle of operation of fixed-bed reactor reach 8800h.
And, can be found out by the result of comparing embodiment 1 and the present embodiment, the present embodiment by the condition of adjustment solvent deasphalting process to make in DAO N.heptane insolubles content lower than 0.1 % by weight time, when using the decalcifying agent of amount in the same manner as in Example 1, calcium contents in decalcification DAO can be made to be reduced to 0.9 μ g/g, and cycle of operation was compared with long more than 40 days of the cycle in embodiment 1.
But the yield of embodiment 1 is high compared with the yield of the present embodiment.Also namely, the process conditions by adjusting method of the present invention can control product property of the present invention and plant running cycle etc. flexibly.
Embodiment 3
The present embodiment is for illustration of the method for calcium contents and the processing and treating method of long residuum in reduction long residuum of the present invention.
The high calcium content long residuum as stock oil selected in the present embodiment is in the same manner as in Example 1.
(1) solvent deasphalting process is carried out to high calcium content long residuum: the various conditions of solvent deasphalting process are all identical with embodiment 1.DAO character is identical with embodiment 1.
(2) decalcification process is carried out to DAO: decalcifying agent consumption is 300 μ g/g; Relative to the DAO of every kg, the add-on of described emulsion splitter is 50mg, and the consumption of described water is 100g; The DAO that decalcifying agent, emulsion splitter, water obtain with step (1) is fully mixed, under 90 DEG C, 250 volts of/centimetre of electric fields, acts on 4h, be then separated decalcification DAO (oil phase) and water (aqueous phase).Analyzing calcium contents in decalcification DAO is 1.7 μ g/g.
(3) bed hydroprocessing process is fixed to decalcification DAO: the reactor that fixed bed hydrogenation process employing is identical with embodiment 1 and condition.Result is: after running 8400h, beds average reaction temperature is 410 DEG C, and total reactor pressure reduces to 0.48MPa, reaches the maximum average temperature that reactor allows, and stops work.
As can be seen from the result of the present embodiment, when adopting the method process long residuum of the present embodiment, the calcium contents in material can be made to reduce by increasing decalcifying agent consumption, and the cycle of operation of fixed-bed reactor reach 8400h.
But, can be found out by the result of comparing embodiment 1 and the present embodiment, the present embodiment by the amount of the decalcifying agent of use 2 doubly in embodiment 1 only can make calcium contents comparatively embodiment 1 reduce by 0.2 μ g/g, running period is compared with cycle stretch-out about the 100h of embodiment 1, from the cost of the decalcifying agent used, adopt the method economic benefit of embodiment 1 higher.
Embodiment 4
The present embodiment is for illustration of the method for calcium contents and the processing and treating method of long residuum in reduction long residuum of the present invention.
The character of the high calcium content long residuum as stock oil selected in the present embodiment is as shown in table 2 below.
(1) carry out solvent deasphalting process to high calcium content long residuum: normal heptane selected by solvent, extraction temperature 240 DEG C, working pressure 5MPa, solvent and atmospheric resid feed volume ratio are 10:1.After extracting, DAO is that in 90.7 % by weight, DAO, N.heptane insolubles content is 0.13 % by weight relative to the yield of long residue feed, and density is 0.94g/mL, and calcium contents is 27.3 μ g/g, and nickel content is 23.5 μ g/g, and content of vanadium is 10.2 μ g/g.
(2) decalcification process is carried out to DAO: decalcifying agent consumption is 150 μ g/g; Relative to the DAO of every kg, the add-on of described emulsion splitter is 50mg, and the consumption of described water is 100g; The DAO that decalcifying agent, emulsion splitter, water obtain with step (1) is fully mixed, under 90 DEG C, 250 volts of/centimetre of electric fields, acts on 4h, be then separated decalcification DAO (oil phase) and water (aqueous phase).Analyzing calcium contents in decalcification DAO is 2.1 μ g/g.
(3) bed hydroprocessing process is fixed to decalcification DAO: in fixed-bed reactor, the kind of loading catalyst, loadings and type of feed are identical with embodiment 1.Hydroprocessing condition is identical with embodiment 1, and when operating initial, beds average reaction temperature is 360 DEG C; Detect sulphur content in hydrogenated residue, if sulphur content is more than 0.4 % by weight in hydrogenated residue, then suitably improve beds average reaction temperature, in control hydrogenated residue, sulphur content is at 0.35-0.4 % by weight.After running 8300h, beds average reaction temperature is 405 DEG C, and total reactor pressure reduces to 0.5MPa, and the maximal pressure reaching reactor permission falls, and stops work.
Table 2 high calcium content long residuum main character
| 20 DEG C of density (kg/m 3) | 956.5 |
| 100 DEG C of viscosity (mm 2/s) | 180.3 |
| S content (% by weight) | 1.5 |
| N content (μ g/g) | 4700 |
| Carbon residue (% by weight) | 12.3 |
| Ni content (μ g/g) | 68.2 |
| V content (μ g/g) | 31.6 |
| Ca content (μ g/g) | 60 |
| Initial boiling point (DEG C) | 350 |
Embodiment 5
The present embodiment is for illustration of the method for calcium contents and the processing and treating method of long residuum in reduction long residuum of the present invention.
The high calcium content long residuum as stock oil selected in the present embodiment is in the same manner as in Example 1.
(1) carry out solvent deasphalting process to high calcium content long residuum: normal hexane selected by solvent, extraction temperature 230 DEG C, working pressure 3MPa, solvent and atmospheric resid feed volume ratio are 8:1.After extracting, DAO is that in 87.2 % by weight, DAO, N.heptane insolubles content is 0.11 % by weight relative to the yield of long residue feed, and density is 0.938g/mL, and calcium contents is 21.3 μ g/g, and nickel content is 23.9 μ g/g, and content of vanadium is 9.2 μ g/g.
(2) decalcification process is carried out to DAO: decalcifying agent consumption is 150 μ g/g; Relative to the DAO of every kg, the add-on of described emulsion splitter is 50mg, and the consumption of described water is 100g; The DAO that decalcifying agent, emulsion splitter, water obtain with step (1) is fully mixed, under 90 DEG C, 250 volts of/centimetre of electric fields, acts on 4h, be then separated decalcification DAO (oil phase) and water (aqueous phase).Analyzing calcium contents in decalcification DAO is 1.5 μ g/g.
(3) bed hydroprocessing process is fixed to decalcification DAO: in fixed-bed reactor, the kind of loading catalyst, loadings and type of feed are identical with embodiment 3.Hydroprocessing condition is: hydrogen dividing potential drop 14.0MPa, mark state hydrogen to oil volume ratio 500:1, volume space velocity 0.25h
-1, when operating initial, beds average reaction temperature is 360 DEG C; Detect sulphur content in hydrogenated residue, if sulphur content is more than 0.40 % by weight in hydrogenated residue, then suitably improve beds average reaction temperature, in control hydrogenated residue, sulphur content is at 0.35-0.40 % by weight.After running 8500h, beds average reaction temperature is 408 DEG C, and total reactor pressure reduces to 0.50MPa, and the maximal pressure reaching reactor permission falls, and stops work.
As can be seen from the result of the present embodiment, when adopting the method process long residuum of the present embodiment, calcium contents in decalcification DAO can be made to reduce, and the cycle of operation of fixed-bed reactor reach 8500h.
But, can be found out by the result of contrast the present embodiment and embodiment 1, the present embodiment is that solvent is when carrying out solvent deasphalting process as solvent with normal hexane, N.heptane insolubles content can be made to reduce more, in decalcification DAO, calcium contents reduces more, catalyzer life cycle slightly extends, but DAO yield comparatively reduces in embodiment 1.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (11)
1. reduce a method for calcium contents in long residuum, it is characterized in that, the method comprises:
(1) long residuum is carried out solvent deasphalting process, obtain deasphalted oil, wherein, the condition controlling solvent deasphalting process makes N.heptane insolubles content in deasphalted oil not higher than 0.3 % by weight;
(2) under aqueous conditions, the deasphalted oil that decalcifying agent and emulsion splitter and step (1) obtain is contacted and carries out oily water separation.
2. method according to claim 1, wherein, in step (1), the condition controlling solvent deasphalting process makes N.heptane insolubles content in described deasphalted oil not higher than 0.1 % by weight.
3. method according to claim 1, wherein, in step (1), the condition controlling solvent deasphalting process makes described deasphalted oil be more than 70% relative to the yield of described long residuum, is preferably more than 80%.
4. according to the method in claim 1-3 described in any one, wherein, in step (1), in described long residuum, in the calcium contents of calcium ion for being not less than 10 μ g/g; Preferably be not less than 20 μ g/g.
5., according to the method in claim 1-3 described in any one, wherein, in step (1), the solvent in described solvent deasphalting process is selected from least one in the alkane of C5-C8, the alkene of C5-C8, condensate oil and petroleum naphtha; Preferably be selected from least one in the alkane of C5-C8; Be more preferably at least one be selected from the alkane of C7.
6. according to the method in claim 1-3 described in any one, wherein, in step (1), the condition of described solvent deasphalting process comprises: temperature is 60-280 DEG C, pressure is 1-6MPa, and the input material volume ratio of solvent and long residuum is 0.5-30:1; Preferably include: temperature is 100-240 DEG C, pressure is 3-5MPa, and the input material volume ratio of solvent and long residuum is 3-15:1.
7., according to the method in claim 1-3 described in any one, wherein, in step (2), relative to the calcium ion of ppm every in deasphalted oil, the consumption of described decalcifying agent is 1-15ppm; Preferable amount is 3-10ppm.
8., according to the method in claim 1-3 described in any one, wherein, in step (2), relative to every kg deasphalted oil, the consumption of described emulsion splitter is 1-1000mg; The consumption of described water is 30-500g.
9., according to the method in claim 1-3 described in any one, wherein, in step (2), the consumption of described decalcifying agent, emulsion splitter and water is not for the calcium contents in the oil phase that obtains after making to carry out oily water separation is higher than 5 μ g/g; Preferably not higher than 2 μ g/g.
10. according to the method in claim 1-3 described in any one, wherein, in step (2), the density of described deasphalted oil is below 0.950g/mL, is preferably below 0.945g/mL.
The processing and treating method of 11. 1 kinds of long residuums, is characterized in that, the method comprises:
(1) long residuum is carried out solvent deasphalting process, obtain deasphalted oil, wherein, the condition controlling solvent deasphalting process makes N.heptane insolubles content in deasphalted oil not higher than 0.3 % by weight;
(2) under aqueous conditions, the deasphalted oil that decalcifying agent and emulsion splitter and step (1) obtain is contacted and carries out oily water separation;
(3) in presence of hydrogen, the material containing the oil phase obtained after step (2) is contacted with hydrogenation catalyst.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87105863A (en) * | 1986-08-28 | 1988-03-30 | 切夫尔昂研究公司 | Decalcification of hydrocarbonaceous feedstocks with sequestrant |
| CN1431277A (en) * | 2002-01-10 | 2003-07-23 | 中国石油化工股份有限公司 | Demetallization agent for hy drocarbon oil and its operation method |
| CN103102944A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Combined process of hydrotreatment and light fraction-conversion for residual oil |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87105863A (en) * | 1986-08-28 | 1988-03-30 | 切夫尔昂研究公司 | Decalcification of hydrocarbonaceous feedstocks with sequestrant |
| CN1431277A (en) * | 2002-01-10 | 2003-07-23 | 中国石油化工股份有限公司 | Demetallization agent for hy drocarbon oil and its operation method |
| CN103102944A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Combined process of hydrotreatment and light fraction-conversion for residual oil |
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