CN1128859C - Converting and combining method for hydrogenation of hydrocarbon - Google Patents
Converting and combining method for hydrogenation of hydrocarbon Download PDFInfo
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- CN1128859C CN1128859C CN 99103876 CN99103876A CN1128859C CN 1128859 C CN1128859 C CN 1128859C CN 99103876 CN99103876 CN 99103876 CN 99103876 A CN99103876 A CN 99103876A CN 1128859 C CN1128859 C CN 1128859C
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Abstract
The present invention relates to a combining method for hydroconversion of hydrocarbons, which comprises: an effluent E1 of a first reaction part R1 of a first hydrocarbon raw material F1 is separated into thermal high-pressure hydrogen-rich gas V1 and thermal high-pressure hydrocarbon liquid L1 in a thermal high-pressure separation part S1; at least one part of the V1 is introduced into a second reaction part R2 of a second hydrocarbon raw material F2, and an effluent E2 of the second reaction part R2 is separated into cold high-pressure hydrogen-rich gas V2 and cold high-pressure hydrocarbon liquid L2 in a cold high-pressure separation part S2; and dissolved hydrogen in L1 is recovered. The present invention has the advantages of hydrogen consumption reduction, high-pressure operation step saving and energy consumption reduction. The present invention is especially suitable for the combination of hydrodesulfurization and hydrocracking.
Description
The invention belongs to the hydrocarbon hydroconversion process, particularly the combined method of hydrocarbon hydroconversion process.
As everyone knows, the hydrocarbon hydroconversion process is the conversion process of the consumption hydrogen of hydrocarbon feed under the hydrogen existence condition, here said hydrocarbon hydroconversion process, its raw material hydrocarbon can be the hydro carbons from oil or coal or oil shale, the cut scope of raw material hydrocarbon from gasoline, kerosene, diesel oil, wax oil up to residual oil, and above-mentioned raw materials sulfur-bearing all in most cases.The hydrocarbon hydroconversion process is being classified as hydrotreatment process, unifining process and hydrocracking process traditionally, though there is no significant line of delimitation between these three kinds of hydroconversion process, well-known difference is arranged on the depth of conversion of raw material.The hydrotreatment process is that demulcent is a kind of in above-mentioned three class processes.The application of unifining process is more extensive than the hydrotreatment process, and has also comprised the hydrotreatment process in a broad sense.Typical unifining process comprises the hydrogenating desulfurization and the hydrodenitrification of hydrocarbon raw material.The wax oil hydrogenation desulfurization is a kind of important unifining process.Hydrocracking process be in above-mentioned three class processes hydrocarbon raw material by maximum a kind of of cracked, it is a raw material with gasoline, kerosene, diesel oil, wax oil and residual oil, is widely used in production liquefied petroleum gas (LPG), catalytic reforming raw material, high-quality intermediate oil, cracking ethylene raw material, WHITE OIL PRODUCTION raw material and lubricated wet goods.
In hydroconversion process, the mixing raw material that contains hydrogen and hydro carbons contacts with catalyzer in one or more reactors, is that 250～530 ℃, pressure are to react under the condition of 1.4～28.0MPa in temperature usually.The typical chemical reaction that hydroconversion process takes place comprises that hydrodemetallation (HDM), hydrogenating desulfurization, hydrogenation are saturated, hydrodenitrification, hydrocracking and hydroisomerization.Hydroconversion reactions part effluent contains unreacted hydrogen, conversion and unconverted hydro carbons and gas products, and these gas products comprise normally gaseous hydrocarbon and foreign gas such as H
2S, NH
3Usually, the hydroconversion process reaction effluent is separated into the hydrogen-rich gas and the hydrocarbon liquid that are circulated to reactive moieties and generates oil, described hydrocarbon liquid generates oil and can be used as product or other hydroconversion process raw material or catalytically cracked material usually after fractionation, especially, in hydrocracking process, it can be liquid product such as light naphthar, heavy naphtha, boat coal, diesel oil and hydrocracking tail oil by fractionation that described hydrocarbon liquid generates oil.The initially-separate of described reaction effluent normally adopts " cold minute flow process " to finish.In cold minute flow process, reaction effluent is cooled to suitable temperature, is generally 25～65 ℃, is separated into then that hydrocarbon liquid generates oil and its hydrogen concentration is enough to be circulated to the hydrogen-rich gas that reactive moieties is used.Flow process can obtain maximum hydrogen recovery rate and raising recycle hydrogen hydrogen concentration by ability and the oily receptivity to hydrogen of reduction generation of reduction separation temperature enhancing generation oil absorption conventional gas component C 1, C2, C3, C4 in cold minute, still lost a considerable amount of heat energy in the reaction effluent.Still have a certain amount of dissolved hydrogen hydrogen loss simultaneously.The another kind of method of finishing the initially-separate of reaction effluent is " a thermoanalysis journey ", it can improve reaction effluent heat energy utilization rate, reduces the reaction effluent cooling load and reduce the cooling heat exchanger area, but, it can reduce the recycle hydrogen hydrogen concentration and increase hydrogen loss, because reaction effluent contains more dissolved hydrogen in the hydrocarbon liquid that high pressure hot separator is discharged.Simultaneously, the thermal high that high pressure hot separator is discharged separates gas and is cooled to certain low temperature and enters cold high pressure separator and finish the hydrogen process of gas-liquid separation to obtain to recycle, and still has the investment of a considerable amount of heat-energy losses and corresponding cooling equipment inevitably.
When refinery or chemical plant when transforming sulfur-bearing wax oil raw material with the cracking of ethylene stock oil of the fraction oil of the low-sulfur catalytic cracking stock oil that obtains hydrodesulfurization process simultaneously and produce and hydrocracking process generation and cracking tail oil or low aromatic index (BMCI value), will face following situation according to prior art: because the reaction depth of two kinds of desired hydroconversion process of product differs greatly, the weight hydrogen consumption difference of its unit weight stock oil is also bigger, can reach 0.1～0.4%, the hydrogen cost of promptly processing raw material per ton differs from 10～40 yuans, therefore, from reducing hydrogen consumption angle, should establish two reactive systems, select the bigger appropriate catalyst separately of performance difference and reaction conditions such as reaction depth for use, liquid hourly space velocity, hydrogen-oil ratio is finished the hydroconversion reactions of expection, but (cover is the wax oil hydrogenation desulfurization to build two covering devices, one cover is the wax oil hydrogenation cracking) investment is bigger, and the increase operating cost; Finish above-mentioned two kinds of targets if reduce investment with the hydroeracking unit of the low relatively transformation efficiency of a cover, then causing its product is the excessive hydrogenation conversion of this part raw material of catalytically cracked stock, and waste hydrogen increases considerably cost.
Have multiple about the combination process that contains two or more hydroconversion process, as method as described in US 2671754, US3026260, US3365388, US3592758, US3655551, the US5026472, its common trait is that the hydrocarbon liquid product of upstream reaction zone effluent sepn process gained carries out the secondary hydrocracking as downstream reaction district hydrocarbon feed.Chinese patent CN1016966B relates to a kind of logistics that will contain heavy hydrocarbon under the hydrogen existence condition and is transformed into the method that contains the low boiling point hydrocarbon logistics, the main conversion fluid stream of its first conversion zone raw material, first section effluent is separated into air-flow and liquid stream at separate part, air-flow enters second conversion zone, and second conversion zone mainly transforms hydro carbons in the air-flow.Above patent does not all relate to the combined method of the bigger hydrocarbon hydroconversion process of raw material weight transformation efficiency difference.
The objective of the invention is to propose a kind of combined method,, realize that reasonably chemistry consumes hydrogen, reduce the high top pressure operation step, cut down the consumption of energy, reduce the dissolved hydrogen loss to realize the combination producing of the hydrocarbon hydroconversion process that the hydrocarbon feed depth of conversion is different.
For reaching above-mentioned purpose, a kind of converting and combining method for hydrogenation of hydrocarbon of the present invention comprises following steps:
(1) in first reactive moieties, first hydrocarbon raw material generates first reaction effluent that contains hydrogen, foreign gas and hydrocarbon compound through hydroconversion reactions under the hydrogen existence condition;
(2) first reaction effluents are finished a thermal high sepn process at the thermal high separate part, generate the thermal high hydrocarbon liquid that a thermal high hydrogen-rich gas that contains most of hydrogen in first reaction effluent, foreign gas and normally gaseous hydrocarbon and a small amount of conventional liquid hydrocarbon and one are contained most of conventional liquid hydrocarbon and dissolved hydrogen in first reaction effluent;
(3) the described thermal high hydrogen-rich gas of at least a portion is imported described second reactive moieties of step (4);
(4) in second reactive moieties, second hydrocarbon raw material generates second reaction effluent that contains hydrogen, foreign gas and hydrocarbon compound through hydroconversion reactions under the hydrogen existence condition; The hydrocarbon feed weight transformation efficiency of described second reactive moieties is higher more than 5% than the hydrocarbon feed weight transformation efficiency of first reactive moieties;
(5) second reaction effluents are finished a cold anticyclone sepn process at the cold anticyclone separate part, generate the cold anticyclone hydrocarbon liquid that a cold anticyclone hydrogen-rich gas that contains most of hydrogen in second reaction effluent, foreign gas and normally gaseous hydrocarbon and a small amount of conventional liquid hydrocarbon and one are contained most of conventional liquid hydrocarbon and solution gas in second reaction effluent.
According to the inventive method, first reaction effluent be cooled be cooled to 150～400 ℃, especially be cooled to 200～350 ℃, preferably be cooled to 250～350 ℃ and enter the thermal high separate part then and separate.
The inventive method is particularly suitable for first reactive moieties and carries out wax oil hydrogenation desulphurization reaction, the cracking reaction of second reactive moieties execution wax oil hydrogenation.
The present invention's first reaction effluent adopts the thermal high sepn process, gained carries the foreign gas of first reactive moieties generation and the thermal high hydrogen-rich gas of normally gaseous hydrocarbon has entered in second reactive moieties as the hot hydrogen raw material under high temperature, condition of high voltage, therefore, one of effect of the present invention has been to avoid the inevitable subcooling process of hydrocarbon hydroconversion process reaction effluent sepn process of routine techniques, can save heat exchange, the cooling apparatus of the sepn process of first reaction effluent, and improve capacity usage ratio; Two of effect of the present invention has been to realize the repeated use of hydrogen, thereby can reduce the recycle hydrogen usage quantity, thereby has reduced the equipment size of hydrogen gas circulating system, reduces investment; Three of effect of the present invention is to make the foreign gas of first reactive moieties generation and the foreign gas and the normally gaseous hydrocarbon of normally gaseous hydrocarbon and the generation of second reactive moieties to concentrate in second reaction effluent, thereby foreign gas such as removing of H2S, NH3 that first, second reactive moieties is produced have been realized concentrated removing, thereby can improve plant factor, reduce facility investment.
Describe the present invention in detail below in conjunction with accompanying drawing.
Accompanying drawing 1 is first kind of scheme schema of the present invention;
Accompanying drawing 2 is second kind of scheme schema of the present invention.
Accompanying drawing is drawn for the present invention is described, but can not limit range of application of the present invention.
First kind of scheme of the present invention as shown in Figure 1, the first hydrocarbon raw material F1 that comes along pipeline 1 with along pipeline 2 and the hydrogen gas stream of coming enters the first reactive moieties R1, under certain effectively operational condition, finish hydroconversion reactions, generate first a reaction effluent E1 who contains hydrogen, foreign gas and hydrocarbon compound; The first reaction effluent E1 enters thermal high separate part S1 along pipeline 4 and finishes a thermal high sepn process, generates the thermal high hydrocarbon liquid L1 that a thermal high hydrogen-rich gas V1 who contains most of hydrogen, foreign gas and normally gaseous hydrocarbon and a small amount of conventional liquid hydrocarbon among the first reaction effluent E1 and are contained most of conventional liquid hydrocarbon (more than 75% weight) and dissolved hydrogen among the first reaction effluent E1; Thermal high hydrogen-rich gas V1 leaves thermal high separate part S1 along pipeline 6, and the described thermal high hydrogen-rich gas of at least a portion V1 imports the described second reactive moieties R2; Shown in the figure is the situation that whole thermal high hydrogen-rich gas V1 import the second reactive moieties R2.The second hydrocarbon raw material F2 that comes along pipeline 7 with along pipeline 6 and the high pressure hydrogen-rich gas V1 that comes and may use along pipeline 8 and other hydrogen-rich gas that comes enters the second reactive moieties R2, under certain effectively operational condition, finish hydroconversion reactions, generate second a reaction effluent E2 who contains hydrogen, foreign gas and hydrocarbon compound; The second reaction effluent E2 enters cold anticyclone separate part S2 along pipeline 12 and finishes a cold anticyclone sepn process, usually generates the cold anticyclone hydrocarbon liquid L2 that a cold anticyclone hydrogen-rich gas V2 who contains most of hydrogen, foreign gas and normally gaseous hydrocarbon and a small amount of conventional liquid hydrocarbon among the second reaction effluent E2 and are contained most of conventional liquid hydrocarbon and solution gas among the second reaction effluent E2 by reducing by the second reaction effluent E2 temperature; Cold anticyclone hydrogen-rich gas V2 leaves cold anticyclone separate part S2 along pipeline 14, and cold anticyclone hydrocarbon liquid L2 leaves cold anticyclone separate part S2 along pipeline 30.
Combined method of the present invention shown in the accompanying drawing 2 is compared with accompanying drawing 1 and is further characterized in that: cold anticyclone hydrogen-rich gas V2 leaves cold anticyclone separate part S2 along pipeline 14, the described cold anticyclone hydrogen-rich gas of at least a portion V2 returns the first reactive moieties R1 and/or the second reactive moieties R2, and shown in the figure is the situation that cold anticyclone hydrogen-rich gas V2 all returns.According to accompanying drawing 2, cold anticyclone hydrogen-rich gas V2 returns to enter before the reactive moieties and takes off H
2S part 15 is taken off H
2After S handles, form and take off H
2The cold anticyclone hydrogen-rich gas of S takes off H
2The cold anticyclone hydrogen-rich gas of S removes the first reactive moieties R1 and the second reactive moieties R2 as recycle hydrogen along pipe 17 and pipe 18 along pipe 16 after the circulating hydrogen compressor supercharging, part recycle hydrogen mixes with the new hydrogen that comes along pipe 20 along pipe 17, gas mixture enters the first reactive moieties R1 along pipe 2, after the new hydrogen that another part recycle hydrogen comes with edge pipe 22 along pipe 18 mixes, enter among the second reactive moieties R2 along pipe 8.Recycle hydrogen also can all enter the first reactive moieties R1 or all enter the second reactive moieties R2 in the pipe 16, and shown in the accompanying drawing 2 is that recycle hydrogen enters the first reactive moieties R1 and the second reactive moieties R2 simultaneously in the pipe 16.The new hydrogen that the present invention uses, according to accompanying drawing 2, edge pipe 19 is divided into two curb pipes 20 after the make-up hydrogen compressor supercharging, pipe 22 removes the first reactive moieties R1 and the second reactive moieties R2; Hydrogen in the pipe 19 also can all enter the first reactive moieties R1 or all enter the second reactive moieties R2, recommends the hydrogen in the pipe 19, all enters in 20 among the first reactive moieties R1 through managing.Further, the thermal high hydrocarbon liquid L1 along pipe 23 leaves thermal high separate part S1, finish a thermal low sepn process at thermal low separate part S3: by reducing thermal high hydrocarbon liquid L1 pressure, flash distillation form one on volumetric concentration mainly by H
2The thermal low gas V3 that forms and a thermal low hydrocarbon liquid L3 who mainly forms by hydrocarbon compound, the 26 thermal low gas V3 that leave thermal low separate part S3 finish a cold low sepn process at cold low separate part S4 along pipe, by reduce thermal low gas V3 temperature form one on volumetric concentration mainly by H
2Cold low hydrogen-rich gas V4 and a cold low hydrocarbon liquid L4 of forming, cold low hydrogen-rich gas V4 leaves cold low separate part S4 along pipe 28, and cold low hydrocarbon liquid L4 leaves cold low separate part S4 along pipe 29; At least a portion cold low hydrogen-rich gas V4 is delivered to the first reactive moieties R1 or and second reactive moieties R2 use.Further, finish a cold anticyclone hydrocarbon liquid L2 cold low flash vaporization process at cold low separate part S5: by reducing the cold anticyclone hydrocarbon liquid L2 pressure that leaves cold anticyclone separate part S2 along pipe 30, flash distillation forms the cold low gas V5 and the cold low hydrocarbon liquid L5 who mainly is made up of hydrocarbon compound that mainly are made up of H2, normally gaseous hydrocarbon, cold low gas V5 leaves cold low separate part S5 along pipe 32, and cold low hydrocarbon liquid L5 leaves cold low separate part S5 along pipe 33.
" hydrocarbon hydroconversion process " speech refers to the process that hydrocarbon raw material is converted into hydrocarbon products under the condition that consumes hydrogen herein, and described hydroconversion process comprises common described hydrocracking treating processes, unifining process and hydrocracking process.The hydroconversion process reaction effluent comprises hydrogen, normally gaseous hydrocarbon, conventional liquid hydrocarbon and foreign gas.
" unifining process " described herein speech refers to its raw material weight transformation efficiency and is not more than 25% hydroconversion process.Generally described " unifining process " speech refers to its raw material weight transformation efficiency and is not more than 15% hydroconversion process, and described especially " unifining process " speech refers to its raw material weight transformation efficiency and is not more than 10% hydroconversion process.
" foreign gas " of the present invention speech refers to the non-hydrocarbon gas that produces that is contained in the reaction effluent in reaction process, such as the H2S and/or the such gas of NH3 of organosulfur in the hydrocarbon raw material and/or the generation of organonitrogen hydrocracking.
" normal boiling point " described herein speech refers to the boiling temperature of material under atmospheric pressure conditions, unless dated especially, boiling point described herein refers to the normal boiling point temperature.Can measure its boiling temperature with the ASTM-D86 method for gasoline and lighter hydro carbons, can test its boiling temperature with the ASTM-D1160 method for heavy gas oil and heavier charging.Gasoline boiling point boiling range is about 80～210 ℃, light gas oil normal boiling point boiling range is about 150～350 ℃, and heavy oil for the normal boiling point boiling range be about 350～540 ℃ gas oil and boiling point at the residual oil more than 350 ℃ and boiling point at the vacuum residuum more than 550 ℃, unless dated especially, the boiling point boiling range refers to the boiling temperature from 5% cut point to 95% cut point.
Hereinafter " the first hydrocracking part " speech refers to, comprise described first reactive moieties R1 and thermal high separate part S1 and the separating step of the L1 that may use in interior process; The L2 flash distillation step that " the second hydrocracking part " comprises the second reactive moieties R2, cold anticyclone separate part S2 and may use.
Need to prove that the use of " the first hydrocracking part ", " the second hydrocracking part " word is just in order to say something, this does not constitute any qualification to actual content of the present invention.
The hydrocarbon feed of process of the present invention can be the hydro carbons from oil or coal or oil bearing rock page or leaf or tar sand.It is 350～550 ℃ of hydrocarbon compositions by boiling spread mainly that the first hydrocarbon raw material F1 can be, and the second hydrocarbon raw material F2 mainly is by 200 ℃～550 ℃ of boiling points, in particular mainly by 300～530 ℃ hydrocarbon composition.Especially, the first hydrocarbon raw material F1 and the second hydrocarbon raw material F2 are with a kind of hydro carbons.
To arbitrary specific hydroconversion process combination, its first reactive moieties R1 is or/and the actually operating condition of the second reactive moieties R2 depends on the condition as feed composition and process unit process function, changes with the character of the reaction depth of raw material properties, expection and the catalyzer that may use.The first reactive moieties R1 or/and the second reactive moieties R2 hydrocracking operational condition comprise from as the required mitigation condition of the unifining process that removes a part of sulphur the light charging such as petroleum naphtha or light gas oil until as the hydrogenating desulfurization of high content of wax VACUUM TOWER BOTTOM material or the severe condition of hydrocracking process.Demulcent hydrofining condition generally include low pressure (1.4～7.0MPa), 1.0h
-1Above liquid hourly space velocity, recycle hydrogen flow rate 35～350Nm
3/ m
3Raw material and the temperature of reaction that is lower than 400 ℃; Harsh hydrocracking condition comprises: the pressure of 14.0～28.0MPa, 400～530 ℃ temperature, 0.2～0.6h
-1Liquid hourly space velocity, recycle hydrogen flow rate 180～3600Nm
3/ m
3Raw material; Suitable hydrogenation conversion condition scope is: the pressure of 3.5～20.0Mpa, 250～460 ℃ temperature, 0.4～2h
-1Liquid hourly space velocity, recycle hydrogen flow rate 180～1800Nm
3/ m
3Raw material.The working pressure of the hydroconversion process of combined method of the present invention recommends to be higher than 2.5MPa.
Disclosed hydrogenation conversion catalyst has multiple, and some appropriate catalyst wherein can be bought from manufacturers.The first reactive moieties R1 is or/and the second reactive moieties R2 catalyst system therefor should be formed and expection process goal and selecting according to raw material, and therefore, the composition variation range of catalyzer is very wide.Typical catalyst is made up of (support) one or more metal components on the inorganics refractory support that distribute, and the metal component on the catalyzer is from the VIII in the periodic table of elements, V and VI family.Selected normally Ni, Co, Mo, Cr and W also contain Fe and Pt sometimes, and the form of the metal on the catalyzer can be metallic element or metal oxide or metallic sulfide or other compound.Every kind of metal content is 0.1～40wt% of catalyzer total amount normally, although the content of metal exceeds above-mentioned scope on some catalyzer.The containing metal compound catalyst generally uses with oxide form, carries out prevulcanized then and handles, and this treating processes can be carried out outside the field of employment, carries out but be preferably within the field of employment, particularly carries out under the condition similar to practical application.Metal component can be attached on the inorganic amorphous carrier, as silicon-dioxide, aluminum oxide or silicon-dioxide-aluminum oxide.Can use various technology, comprise dipping, soak and be total to mulling, metal component is attached on the refractory oxide.In hydrocracking used catalyzer can be amorphous but zeolite type preferably.Verified, the y-type zeolite of y-type zeolite and modern modification is good especially catalyzer in hydrocracking process.In addition, can comprise dipping and ion-exchange, metal component is attached on the zeolite by any technology known in the art.For some hydrocracking process, except that zeolite, in catalyzer, also may use amorphous silicas-aluminum oxide, and the tackiness agent that in this class catalyzer, usually adopts.
According to the present invention, the first reactive moieties R1 carries out hydrofining reaction process or the hydrodesulfurization reaction process of the first hydrocarbon raw material F1, can obtain good especially effect and the second reactive moieties R2 carries out the hydrocracking reaction process of the second hydrocarbon raw material F2.
According to the present invention, the service temperature of the first reactive moieties R1 250 ℃～480 ℃ especially between 300～440 ℃, the first reaction effluent E1 be cooled be cooled to 150～400 ℃, especially be cooled to 200～350 ℃, preferably be cooled to 250～350 ℃ and enter then among the thermal high separate part S1 and separate.According to the present invention, pressure from the thermal high hydrogen-rich gas V1 of thermal high separate part S1 should be approaching with the top hole pressure of the first reactive moieties R1 as far as possible, pressure difference value between the two should determine on demand, generally should not be higher than 0.4MPa, should not be higher than 0.2MPa especially.
According to the present invention, the thermal high hydrogen-rich gas V1 that contains most of hydrogen, foreign gas, normally gaseous hydrocarbon and a small amount of conventional liquid hydrocarbon among the first reaction effluent E1 has entered among the second reactive moieties R2 that transforms the second hydrocarbon raw material F2, and the conversion product of thermal high hydrogen-rich gas V1 and unconverted thing have finally entered cold anticyclone separate part S2 as the conversion product of other charging of the part of the second reaction effluent E2 and the second reactive moieties R2.Therefore the present invention has realized the repeated use of hydrogen, and the foreign gas and the normally gaseous hydrocarbon of the first reactive moieties R1 and second reactive moieties R2 generation concentrated among the second reaction effluent E2.
According to the present invention, the second reactive moieties R2 preferably carries out the hydrocracking reaction of the second hydrocarbon raw material F2.According to the present invention, the service temperature of the second reactive moieties R2 250～480 ℃, especially between 300～440 ℃.According to the present invention, the second reaction effluent E2 is separated into cold anticyclone hydrogen-rich gas V2 and cold anticyclone hydrocarbon liquid L2 at cold anticyclone separate part S2.The service temperature of cold anticyclone separate part S2 below 100 ℃, especially be generally 25～90 ℃, be preferably 30～60 ℃, the working pressure of cold anticyclone separate part S2, should be approaching as far as possible with the top hole pressure of the second reactive moieties R2, pressure difference value between the two should determine on demand, generally be not higher than 1.5MPa, especially be not higher than 1.0MPa, preferably be not higher than 0.7MPa.
According to accompanying drawing 2 of the present invention, at least a portion cold anticyclone hydrogen-rich gas V2 is returned the first reactive moieties R1 or/and the second reactive moieties R2 recycles.Under the situation of recommending, particularly carry out under the situation of hydrodesulfurization reaction at the first reactive moieties R1, cold anticyclone hydrogen-rich gas V2 is earlier through taking off H
2The S treating part generates one and takes off H
2The cold anticyclone hydrogen-rich gas of S also returns reactive moieties, and the depriving hydrogen sulphide method of recommendation is an amine liquid absorption process.According to the present invention, the hydrogen volume concentration from the hydrogen gas stream of cold anticyclone separate part S2 of returning reactive moieties should not be lower than 70%, should not be lower than 75% especially, preferably be not less than 80%.
According to accompanying drawing 2 of the present invention, the hydrogen volume concentration that enters the cold low hydrogen-rich gas V4 of reactive moieties should not be lower than 75%, should not be lower than 80% especially, these hydrogen-rich gases are from the separating step of thermal high hydrocarbon liquid L1: thermal high hydrocarbon liquid L1 is depressurized under 0.5～5.0MPa pressure condition, temperature be generally 150～400 ℃, especially be 200～400 ℃, be preferably under 250～350 ℃ the condition, enter thermal low separate part S3, at this, thermal high hydrocarbon liquid is separated into thermal low hydrogen-rich gas V3 and thermal low hydrocarbon liquid L3.Thermal low hydrogen-rich gas V3, keeping under the constant substantially condition of its pressure, cool to below 100 ℃, reduce to 25～85 ℃, preferably 30～65 ℃ especially, enter cold low separate part S4 then, and be separated into cold low hydrogen-rich gas V4 and cold low hydrocarbon liquid L4.
According to accompanying drawing 2 of the present invention, the operational condition of thermal high separate part S1, thermal low separate part S3, cold low separate part S4, under the condition of recommending, the volumetric concentration that should guarantee hydrogen among the cold low hydrogen-rich gas V4 is not less than 75% or higher, wherein, the temperature of the temperature of thermal low separate part S3 and thermal high separate part S1 is basic identical, and the pressure of the pressure of cold low separate part S4 and thermal low separate part S3 is basic identical.The present invention can reduce the device hydrogen loss by reclaiming the dissolved hydrogen among the hydrocarbon liquid L1.
According to the present invention, cold anticyclone hydrocarbon liquid L2 is depressurized to 0.5～5.0MPa and forms gas, the logistics of liquid mixed phase under the constant substantially condition of holding temperature, enters cold low separate part S5 then and is separated into cold low gas V5 and cold low hydrocarbon liquid L5.The working pressure of cold low separate part S5 is compared basic identical or lower slightly 0.3～1.4MPa with the working pressure of cold low separate part S4.When not using the second cold low separate part S5 step, cold anticyclone hydrocarbon liquid L2 may import such as in the such further course of processing of fractionation, but exemplary application low pressure separate part S5.
Each step of the present invention is temperature and pressure condition such as following table preferably:
280～460 ℃ of 3.5～20.0MPa of the first reactive moieties R1
200～400 ℃ of 3.5～20.0MPa of thermal high separate part S1
280～460 ℃ of 3.5～20.0MPa of the second reactive moieties R2
35～60 ℃ of 3.5～20.0MPa of cold anticyclone separate part S2
200～400 ℃ of 0.5～5.0MPa of thermal low separate part S3
35～60 ℃ of 0.5～5.0MPa of cold low separate part S4
35～60 ℃ of 0.5～5.0MPa of cold low separate part S5
The present invention first reactive moieties R1 carries out the wax oil hydrogenation desulphurization reaction, can obtain good especially effect under the situation of second reactive moieties R2 execution wax oil hydrogenation cracking reaction, and each step of the present invention's this moment is temperature and pressure condition such as following table preferably:
300～440 ℃ of 3.5～15.0MPa of the first reactive moieties R1
250～350 ℃ of 3.5～15.0MPa of thermal high separate part S1
300～440 ℃ of 3.5～15.0MPa of the second reactive moieties R2
35～60 ℃ of 3.0～15.0MPa of cold anticyclone separate part S2
250～350 ℃ of 1.5～4.5MPa of thermal low separate part S3
35～60 ℃ of 1.5～4.5MPa of cold low separate part S4
35～60 ℃ of 1.2～4.5MPa of cold low separate part S5
And the first hydrocarbon feed F1 is 350～550 ℃ of hydrocarbon compositions by boiling point mainly.
New hydrogen volume concentration should greater than 90% (volume), especially greater than 95% (volume), more preferably greater than 98% (volume).
The oil of the reaction effluent E1 of the present invention's first hydrocracking part, the gas sepn process is the thermoanalysis journey, but thermal high separates the foreign gas that generates from the first hydrogenation reaction part R1 among the gas V1 and the eliminating of normally gaseous hydrocarbon, mainly not to utilize the generation oil of first hydrocracking part to be solvent, but mainly utilize the generation oil of second hydrocracking part to be solvent, oil at second hydrocracking, the second reaction effluent E2 partly, be dissolved in the gas sepn process (cold anticyclone sepn process) mainly by the second hydrocarbon raw material F2 in the cold anticyclone hydrocarbon liquid L2 that the generation oil that the second reactive moieties R2 generates is formed, thereby realized that thermal high separates separating of the foreign gas that generates from the first hydrogenation reaction part R1 and normally gaseous hydrocarbon and circulating hydrogen among the gas V1, therefore, the present invention is more suitable for carrying out the low-conversion reaction in the first reactive moieties R1, such as, utilize the very high Hydrobon catalyst of desulfuration selectivity to carry out the wax oil hydrogenation sweetening process, can obtain the reduction hydrogen consumption, improve the unusual effect of capacity usage ratio and minimizing high top pressure operation step.
In the present invention's second hydrocracking part, the raw material oil-hydrogen mixture contacts the effect of generation expection with catalyzer under the hydrocracking condition, and produce the logistics that one is referred to as reaction effluent usually, usually this logistics is at first carried out heat exchange with one or more strands of materials, then, reaction effluent further cools to about 50 ℃ lesser temps by interchanger, air-cooler or watercooler.At last, through cooled mixed phase logistics, its gas phase is by a large amount of H
2And H
2S, H
2O, lighter hydrocarbons such as C
1, C
2Deng composition, its liquid phase is made up of the hydrocarbon or the hydrocarbon compound of condensation, in the reaction effluent liquid phase water is arranged usually.Then, described mixed phase logistics enters a gas, liquid/gas separator.At this, as circulating hydrogen, the liquid phase of telling goes separate part to reclaim product to the gas of telling after possible processing.Sometimes technical process is not directly to cool off and the single-stage separation method, but more complicated separation method such as US3402122, US3586619, US3371029, US3371030, US4159937, US384799 or the described method of Chinese patent CN8919875.Second transform portion of flow process of the present invention, its reaction effluent separation method can use any suitable separation method, for example can be cold minute flow process or thermoanalysis journey.Owing to contain H in the reaction effluent
2S, NH
3Even HCl is arranged, and therefore when cooling off, it can form solid precipitation (amassing), and these sedimentary major ingredient are NH
4Cl and/or many sulphur ammonia.These precipitations can reduce the heat exchanger rate of heat transfer and cause the pressure drop that exceeds the quata.The empirical method of most process using be in the interchanger upstream in reaction effluent the injecting steam water of condensation become to prevent precipitation form so that described solid precipitation is flushed out interchanger.Water in the reaction effluent may also comprise water that raw material oxycompound hydrocracking generates or/and as the water that carries of stock oil.The cooling reaction effluent can generate one usually and contain by H in the reaction effluent
2S, NH
3Separable (free) water of the mixture of the soluble salt compounds that generates.
A kind of hydrocarbon hydroconversion process mode is the secondary hydrocracking, liquid phase stream that the high-pressure separator of first step hydroconversion zone is told and the second stage hydroconversion zone that enters the downstream after the hydrogen make-up of some amount is mixed, described second stage hydroconversion zone can be operated under similar or significantly different conditions, and can use the catalyzer that is different from the use of first step hydroconversion zone.For example, heavy oil fraction at first carries out the hydrocracking demetalization at first step hydroconversion zone, and the liquid-phase product of first step hydroconversion zone enters second stage hydroconversion zone reactor to carry out hydrogenating desulfurization or hydrocracking then.Up to now, a kind of or two kinds of hydrocracking technical process partly of existing multiple different use.The variation of technical process has: the reactor in product to the first district in a circulation part first district or the specific product in a part of second district of circulation (generally be heavy component) are to the reactor in first district.Flow process of the present invention can be applicable to various possible modified flow, and the present invention can be used for the first step or the second stage of secondary hydroconversion process.
The method that accompanying drawing 2 is described comprises that also the heat of the overhead stream V3 that leaves thermal low separate part S3 gets rid of (recovery of transfer) and be converted to the energy recovery of the logistics of low pressure from high pressure, to improve energy utilization efficiency.The conventional equipment of use as interchanger and turbine is to reclaim these energy from process.
When the second reactive moieties R2 of second transform portion uses a plurality of reactor, thermal high separates gas V1 can enter arbitrary reactor inlet, or enter the second reactive moieties R2 and contact with its beds with any other effective means, V1 contacts the mode of the second reactive moieties R2 beds, is not subjected to any restriction.
Embodiment
First hydroconversion process, its hydrocarbon raw material F1 is that boiling range is 350～530 ℃ a wax oil, the F1 sulphur content is greater than 2.0% weight, F1 flow rate 125t/h, it is to carry out in the reactor of hydrogenation conversion catalyst bed of main purpose that the F1 hydroconversion reactions is provided with the hydrogenating desulfurization at one, and the hydrocracking wax oil that the sulphur content of production is lower than 2000PPm can be made catalytic cracking unit stock oil and use.
Second hydroconversion process, its hydrocarbon raw material F2 are that boiling range is 340～525 ℃ of wax oils, and the F2 sulphur content is greater than 2.0% weight, F2 flow rate 188t/h.The F2 hydrocracking reaction carries out in two placed in-line reactors, that reactor that F2 at first passes through is provided with hydrocracking catalyst for demetalation bed and hydrocracking denitrification catalyst bed, this reactor task is a production denitrogenation oil, the hydrocarbon feed chemical hydrogen consumption of denitrification process is than the first hydroconversion process hydrocarbon feed chemical hydrogen consumption high by 0.35% (to hydrocarbon feed weight), use as second reactor feed, the target of second reactor is to make denitrogenation oil mid-boiling point in 350 ℃ of fractions, 50% (weight) of having an appointment is converted into boiling point and is lower than 350 ℃ conversion product, and second reactor is provided with the cracking catalyst bed.
By the present invention, above-mentioned two processes are combined now, the main operational condition of its each step sees the following form:
The scope preferred values first reactive moieties R1
Temperature ℃ 300～460 340～430
500: 1 second reactive moieties R2 of inlet hydrogen to oil volume ratio
Inlet/outlet temperature ℃ 300～460 340～430 thermal high separate part S1:
Temperature ℃ 200～380 300～350
Pressure MPa 3.5～18.0 8.0～13.0 cold anticyclone separate part S2 temperature ℃ 40～65 50 thermal low separate part S3 temperature/pressure ℃/Mpa 200～380/1～4 300～350/2.7 cold low separate part S4 temperature/pressure ℃/MPa 40～65/1～4 38/2.5 cold low separate part S5 temperature/pressure ℃/MPa 40～65/1.5～4 50/2.0
According to the embodiment of above-mentioned condition operation, the cold low hydrogen-rich gas V4 that discharges from cold low separate part S4 is recovered and returns reactive moieties and use, and its hydrogen volume concentration is about 78%, the about 2400NM of flow
3/ h, the wherein about 174kg/h of hydrogen component.
In the present embodiment, the cold anticyclone hydrogen-rich gas that obtains from cold anticyclone separate part S2 returns reactive moieties and recycles, the about 330000Nm of its flow rate after being the depriving hydrogen sulphide treating part of solvent with aqueous alkanolamine
3/ h, its hydrogen component volumetric concentration can reach 80%.
Clearly, build two covers device independent of each other with the branch of routine and compare, embodiment has realized effect of the present invention, mainly shows:
(1) thermal high that has saved first transform portion separate air cooling but, separation, depriving hydrogen sulphide, loop compression, heating step, very natural, equipment and material such as relevant high-tension apparatus, unit, pipeline, instrument and correlation engineering are saved;
(2) avoided thermal high separate gas V1 experience use air cooling and or 150～50 ℃ temperature-fall period of watercooler, thereby reduce the about 3140kw of power loss, and can be converted into 330 ℃ high potential temperature heat energy, be equivalent to save the fuel 240kg/h that calorific value is 41800KJ/kg, go into operation per year and counted in 8000 hours, close fuel 1920t/a;
(3) save the about 54000Nm of recycle hydrogen amount
3/ h;
(4) reclaim dissolved hydrogen 174kg/h;
(5) construction investment can be saved more than 4,000 ten thousand yuans.
If consider that the present invention improves unit scale, thereby reduce the general facilities investment, superiority of the present invention is just more outstanding.
Although present embodiment statement is to be the combination of the hydroconversion process and the hydrocracking process of hydrogenating desulfurization with the main purpose, the invention effect that it is indicated is present in the combination of other any suitable hydrocarbon hydroconversion process equally.
Claims (23)
1. a converting and combining method for hydrogenation of hydrocarbon is characterized in that, comprises following steps:
(1) at the first reactive moieties R1, the first hydrocarbon raw material F1 generates first a reaction effluent E1 who contains hydrogen, foreign gas and hydrocarbon compound through hydroconversion reactions under the hydrogen existence condition;
(2) first reaction effluent E1 finish a thermal high sepn process at thermal high separate part S1, generate a thermal high hydrogen-rich gas V1 who contains most of hydrogen, foreign gas and normally gaseous hydrocarbon and a small amount of conventional liquid hydrocarbon among the first reaction effluent E1 and one and contain the thermal high hydrocarbon liquid L1 of most of conventional liquid hydrocarbon and dissolved hydrogen among the first reaction effluent E1, the service temperature of thermal high separate part S1 is 150～400 ℃;
(3) the described thermal high hydrogen-rich gas of at least a portion V1 is imported the described second reactive moieties R2 of step (4);
(4) at the second reactive moieties R2, the second hydrocarbon raw material F2 generates second a reaction effluent E2 who contains hydrogen, foreign gas and hydrocarbon compound through hydroconversion reactions under the hydrogen existence condition; The hydrocarbon feed weight transformation efficiency of the described second reactive moieties R2 is higher more than 5% than the hydrocarbon feed weight transformation efficiency of the first reactive moieties R1;
(5) second reaction effluent E2 finish a cold anticyclone sepn process at cold anticyclone separate part S2, generate the cold anticyclone hydrocarbon liquid L2 that a cold anticyclone hydrogen-rich gas V2 who contains most of hydrogen, foreign gas and normally gaseous hydrocarbon and a small amount of conventional liquid hydrocarbon among the second reaction effluent E2 and are contained most of conventional liquid hydrocarbon and solution gas among the second reaction effluent E2.
2. combined method according to claim 1, its feature further is: the described cold anticyclone hydrogen-rich gas of at least a portion V2 is returned the first reactive moieties R1 or/and the second reactive moieties R2 recycles.
3. combined method according to claim 1, its feature further is: at least a portion cold anticyclone hydrogen-rich gas V2 is first through taking off H
2S treating part 15 removes H
2Behind the S, form one and remove H
2The hydrogen-rich gas of S also returns the first reactive moieties R1 or/and the second reactive moieties R2 recycles.
4. combined method according to claim 2, its feature further is: the hydrogen volume concentration of described cold anticyclone hydrogen-rich gas V2 is not less than 70%.
5. combined method according to claim 2, its feature further is: the hydrogen volume concentration of described cold anticyclone hydrogen-rich gas V2 is not less than 75%.
6. according to claim 1 or 2 or 3 or 4 or 5 described combined methods, its feature further is: the first reactive moieties R1 carries out the hydrofining reaction process of the first hydrocarbon raw material F1 and the second reactive moieties R2 carries out the hydrocracking reaction process of the second hydrocarbon raw material F2.
7. combined method according to claim 6, its feature further is: the first reactive moieties R1 carries out the hydrodesulfurization reaction process of the first hydrocarbon raw material F1.
8. according to claim 1 or 2 or 3 or 4 or 5 described combined methods, its feature further is: the service temperature of the first reactive moieties R1 is 250 ℃～480 ℃, and working pressure is 3.5～20.0MPa; The service temperature of the second reactive moieties R2 is 250～480 ℃, and working pressure is 3.5～20.0MPa; The service temperature of cold anticyclone separate part S2 is below 100 ℃.
9. combined method according to claim 8, its feature further is: the service temperature of the first reactive moieties R1 is 300 ℃～440 ℃, and working pressure is 3.5～15.0MPa; Thermal high separate part S1 service temperature is 250～350 ℃; The service temperature of the second reactive moieties R2 is 300～440 ℃, and working pressure is 3.5～15.0MPa; The service temperature of cold anticyclone separate part S2 is 30～65 ℃.
10. according to claim 1 or 2 or 3 or 4 or 5 described combined methods, its feature further is: the first hydrocarbon raw material F1 is 350～550 ℃ of hydrocarbon compositions by boiling spread mainly, and the second hydrocarbon raw material F2 is 300～530 ℃ of hydrocarbon compositions by boiling spread mainly.
11. according to claim 1 or 2 or 3 or 4 or 5 described combined methods, its feature further is: the first hydrocarbon raw material F1 and the second hydrocarbon raw material F2 are with a kind of hydro carbons.
12. combined method according to claim 2, its feature further is: the step that comprises dissolved hydrogen among the recovery thermal high hydrocarbon liquid L1 as described below:
Thermal high hydrocarbon liquid L1 finishes a thermal low sepn process at thermal low separate part S3: by reducing thermal high hydrocarbon liquid L1 pressure, flash distillation form one on volumetric concentration mainly by H
2The thermal low gas V3 that forms and a thermal low hydrocarbon liquid L3 who mainly forms by hydrocarbon compound;
Thermal low gas V3 finishes a cold low sepn process at cold low separate part S4: by reduce thermal low gas V3 temperature form one on volumetric concentration mainly by H
2Cold low hydrogen-rich gas V4 and a cold low hydrocarbon liquid L4 of forming;
At least a portion cold low hydrogen-rich gas V4 is delivered to the first reactive moieties R1 or/and the second reactive moieties R2 uses.
13. combined method according to claim 12, its feature further is: at least a portion cold anticyclone hydrogen-rich gas V2 is formed one earlier remove the hydrogen-rich gas of H2S and return the first reactive moieties R1 or/and the second reactive moieties R2 recycles after taking off the H2S treating part to remove H2S.
14. combined method according to claim 12, its feature further is: the hydrogen volume concentration of described cold anticyclone hydrogen-rich gas V2 is not less than 70%.
15. combined method according to claim 12, its feature further is: the hydrogen volume concentration of described cold anticyclone hydrogen-rich gas V2 is not less than 75%.
16. combined method according to claim 12, its feature further is: the hydrogen volume concentration of described cold low hydrogen-rich gas V4 is not less than 75%.
17. combined method according to claim 12, its feature further is: the hydrogen volume concentration of described cold low hydrogen-rich gas V4 is not less than 80%.
18. according to claim 12 or 13 or 14 or 15 or 16 or 17 described combined methods, its feature further is: the first reactive moieties R1 carries out the hydrofining reaction process of the first hydrocarbon raw material F1 and the second reactive moieties R2 carries out the hydrocracking reaction process of the second hydrocarbon raw material F2.
19. combined method according to claim 18, its feature further is: the first reactive moieties R1 carries out the hydrodesulfurization reaction process of the first hydrocarbon raw material F1.
20. according to claim 12 or 13 or 14 or 15 or 16 or 17 described combined methods, its feature further is: the service temperature of the first reactive moieties R1 is 250 ℃～480 ℃, and working pressure is 3.5～20.0Mpa; Thermal high separate part S1 service temperature is 150～400 ℃; The service temperature of the second reactive moieties R2 is 250～480 ℃, and working pressure is 3.5～20.0Mpa; The service temperature of cold anticyclone separate part S2 is below 100 ℃.
21. combined method according to claim 20, its feature further is: the service temperature of the first reactive moieties R1 is 300 ℃～440 ℃, and working pressure is 3.5～15.0Mpa; Thermal high separate part S1 service temperature is 250～350 ℃; The service temperature of the second reactive moieties R2 is 300～440 ℃, and working pressure is 3.5～15.0Mpa; The service temperature of cold anticyclone separate part S2 is 30～65 ℃.
22. require 12 or 13 or 14 or 15 or 16 or 17 described combined methods according to claim, its feature further is: the first hydrocarbon raw material F1 is 350～550 ℃ of hydrocarbon compositions by boiling spread mainly, and the second hydrocarbon raw material F2 is for being 300～530 ℃ of hydrocarbon compositions by boiling spread mainly.
23. according to claim 12 or 13 or 14 or 15 or 16 or 17 described combined methods, its feature further is; The first hydrocarbon raw material F1 and the second hydrocarbon raw material F2 are with a kind of hydro carbons.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99103876 CN1128859C (en) | 1999-03-08 | 1999-03-08 | Converting and combining method for hydrogenation of hydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99103876 CN1128859C (en) | 1999-03-08 | 1999-03-08 | Converting and combining method for hydrogenation of hydrocarbon |
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|---|---|
| CN1260376A CN1260376A (en) | 2000-07-19 |
| CN1128859C true CN1128859C (en) | 2003-11-26 |
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|---|---|---|---|
| CN 99103876 Expired - Lifetime CN1128859C (en) | 1999-03-08 | 1999-03-08 | Converting and combining method for hydrogenation of hydrocarbon |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101173189B (en) * | 2006-11-01 | 2010-05-12 | 中国石油化工股份有限公司 | Two-stage hydrogenation cracking method for producing industrial chemicals |
| CN101412928B (en) * | 2007-10-18 | 2013-01-09 | 中国石油化工股份有限公司 | Hydro-desulphurizing combined method |
| CN101412926B (en) * | 2007-10-18 | 2013-01-09 | 中国石油化工股份有限公司 | Hydro-upgrading combined method |
| CN101412924B (en) * | 2007-10-18 | 2013-03-20 | 中国石油化工股份有限公司 | Unionfining technological process |
| CN102465020B (en) * | 2010-11-05 | 2014-08-20 | 中国石油化工股份有限公司 | Combined hydrofining method |
| CN102146298A (en) * | 2011-02-19 | 2011-08-10 | 何巨堂 | Hydrocarbon hydrogenation conversion process combined method |
| CN102399584B (en) * | 2011-10-12 | 2014-06-25 | 中国石油化工股份有限公司 | Hydrogen combined optimized utilization technology of hydrogenation apparatus |
| CN116286087A (en) * | 2023-03-30 | 2023-06-23 | 恒力石化（大连）炼化有限公司 | Method for producing high-quality industrial white oil by wax oil hydrocracking device |
-
1999
- 1999-03-08 CN CN 99103876 patent/CN1128859C/en not_active Expired - Lifetime
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