CN101629099A - Method for coal tar hydrogenation transformation - Google Patents
Method for coal tar hydrogenation transformation Download PDFInfo
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- CN101629099A CN101629099A CN200810215261A CN200810215261A CN101629099A CN 101629099 A CN101629099 A CN 101629099A CN 200810215261 A CN200810215261 A CN 200810215261A CN 200810215261 A CN200810215261 A CN 200810215261A CN 101629099 A CN101629099 A CN 101629099A
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Abstract
The invention relates to a two-phase method for coal tar hydrogenation transformation. Coal-tar hydrocarbons are converted into a hydrofining reaction effluent in which the common boiling points of the hydrocarbons are all below 370 DEG C in a hydrofining part and at least one kind of hydrofined diesel oil is obtained by separation; and at least part of the hydrofined diesel oil is converted into a hydro-upgrading reaction effluent in hydro-upgrading part and hydro-upgraded diesel oil is obtained by separation. The method is suitable for producing a diesel component with high cetane number and combined processing of coal tar naphtha and coal tar diesel oil.
Description
Technical field
The present invention relates to the hydrogenating conversion process of a kind of high nitrogen-containing, high aromaticity content hydro carbons; Say especially to the present invention relates to a kind of coal tar hydro carbons two-stage method hydrogenating conversion process that the conventional boiling point of institute's hydrocarbon-containifirst all is lower than 370 ℃ in the hydrofining reaction effluent.
Background technology
Two-stage method hydrogenation process of the present invention comprises hydrofining--hydro-upgrading two portions.
Coal tar hydro carbons of the present invention refers in the hydrofining reaction effluent the conventional boiling point of institute's hydrocarbon-containifirst and all is lower than 370 ℃ coal tar hydro carbons.Because the coal tar hydro carbons is in unifining process, it is done and can reduce significantly such as 20 ℃ of reductions, so feed coal tar hydro carbons is done higher such as high 20 ℃ than 370 ℃.
Coal tar of the present invention refers to the coal tar that pyrolysis of coal or coal generating gas or other process produce.Therefore, described coal tar can be the coalite tar cut that produces of coal generating gas, also can be the coalite tar that produces of pyrolysis of coal process (comprising semi-coking, middle temperature coking, high-temperature coking process) or the cut of coal-tar middle oil or coal-tar heavy oil that coal tar of the present invention can also be the mixing oil of above-mentioned coal tar.Because naphthalene price height (about 7000 yuan/ton) for the coal-tar heavy oil lighting end, enters before the hydrogenation unit, naphthalene is wherein reclaimed usually.
For coalite tar, comprise light oil, middle oil, heavy oil usually.The coal tar heavy oil that is higher than 370～390 ℃ in the coalite tar heavy oil is a coal-tar pitch, and very easily coking is not suitable for doing hydrogenating materials.Its conventional boiling point be lower than 390 ℃ coal tar hydro carbons can be usually described in oil (such as 140～390 ℃ of conventional boiling points) and or heavy oil in than light constituent (such as 170～390 ℃ of conventional boiling points).Conventional boiling point of the present invention is lower than 390 ℃ coal tar hydro carbons, also can be the middle oil and or the lighting end of heavy oil of mixing refining light oil (such as 55～190 ℃ of conventional boiling points).
The hydrocarbon hydrocrackings such as oxygen enrichment coal tar that are lower than 390 ℃ at conventional boiling point are produced in the process of diesel component, the cut experience deep hydrofinishing process of high boiling point (being higher than 300 ℃ such as conventional boiling point) is finished deoxidation, desulfurization, denitrogenation, after part aromatic hydrocarbons is saturated, also must experience hydrocracking process finish degree of depth aromatic hydrocarbons saturated and or part open loop cracking after, just can be converted into suitable diesel component, but oxygen enrichment coal tar raw material hydrotreated product water-content height, refining and cracking process unsuitable (even can not) employing one-stage serial flow process (cracking catalyst is caused the hydrothermal deactivation effect, and catalyst life obviously shortens).Water in the hydrotreated product should be removed, then the dehydration hydrogenation refined products is carried out hydrocracking.
Be lower than in the hydrocracking process of 390 ℃ coal tar or other high nitrogen-containing, high aromaticity content hydrocarbon production diesel component at conventional boiling point, because raw material nitrogen content height, stock oil hydrotreated product ammonia content height, as adopting " hydrofining+hydrocracking " one-stage serial flow process, ammonia content height in the cracking catalyst charging, cracking reaction process ammonia dividing potential drop height will reduce the cracking catalyst activity, thereby increase cracking catalyst quantity, increase construction investment greatly.Ammonia removal in the hydrotreated product should be carried out hydrocracking to the deamination hydrotreated product then.
The coal tar hydrogenation modification that is lower than 390 ℃ at conventional boiling point is produced in the process of diesel component, and the cut of conventional low-boiling (such as being lower than 300 ℃) experience deep hydrofinishing process can finish that deoxidation, desulfurization, denitrogenation, part aromatic hydrocarbons are saturated to be converted into suitable diesel component; And the cut of high (such as being higher than 300 ℃) of conventional boiling temperature experience deep hydrofinishing process finish deoxidation, desulfurization, denitrogenation, part aromatic hydrocarbons saturated after, after also must experiencing hydrocracking process and finishing the saturated and part open loop cracking of degree of depth aromatic hydrocarbons, just can be converted into suitable diesel component.Therefore, the process that diesel component is produced in the hydrocracking of wide fraction coal tar raw material is bigger to hydrogenation depth difference light, that last running requires, after the experience deep hydrofinishing process, should carry out hydrocracking to last running separately, promptly require light, last running in the hydrotreated product are separated, then hydro-upgrading is carried out in the last running of hydrotreated product.
Patent CN1676583A, CN100345946C, CN1952071A, CN101033409A, CN101041783, CN101240191A, CN101240192A, CN101240193A etc. disclose the two-stage method hydrogenating conversion process of handling coal tar, the conventional boiling point of contained part hydro carbons is higher than 370 ℃ in the hydrofining reaction effluent, its fractionation by distillation process comprises the sepn process of diesel oil and heavy oil inevitably, diesel component need experience vaporescence could be separated with heavy oil, energy consumption is huge, simultaneously, because heavy constituent metal content height in the full cut of coal tar, hydrogen richness is low, burnt matter and the very easily coking of asphalt content height cause the device cycle of operation short, the hydrogen consumption is high, energy consumption is big.
About the conventional boiling point of its hydrofining reaction effluent institute hydrocarbon-containifirst all be lower than 370 ℃ coal tar hydro carbons two-stage method hydrogenating conversion process, do not appear in the newspapers.
The method that patent CN1147575C coal tar hydrogenating is produced diesel oil, the cetane value that conventional boiling point is lower than the diesel component product that 370 ℃ coal tar hydro carbons produces through one stage hydrofining is lower, during as vehicle fuel, need the high hexadecane value petroleum base diesel component amount of allotment big.
The method of a patent CN1952042A coal tar hydrogenation for producing low solidifying point diesel oil, the coal tar diesel oil distillate is through one stage hydrofining and hydro-upgrading isomerization-visbreaking explained hereafter low-coagulation diesel oil component product, that uses contains β zeolite hydrotreating catalyst, when processing needs the diesel oil heavy constituent of cracking, open loop, also petroleum naphtha component and diesel oil light constituent have been carried out unwanted cracking, open loop inevitably, so diesel yield or liquid yield reduction.Sometimes the conventional boiling point handled of full scale plant is lower than that petroleum naphtha content reaches 15～35% (weight) in 370 ℃ the coal tar hydro carbons, and this moment, the defective of above-mentioned patented method was more obvious.
The object of the present invention is to provide the conventional boiling point of a kind of its hydrofining reaction effluent institute hydrocarbon-containifirst all to be lower than 370 ℃ coal tar hydro carbons hydrofining--hydro-upgrading two-stage method hydrogenating conversion process, hydrofining diesel oil process hydro-upgrading part upgrading is to improve cetane value and or reduction density.
Therefore, first purpose of the present invention is to provide a kind of coal tar hydro carbons two-stage method hydrogenating conversion process, and the conventional boiling point of its hydrofining reaction effluent institute hydrocarbon-containifirst all is lower than 370 ℃.
Second purpose of the present invention is to provide a kind of oxygen enrichment hydrocarbon hydro-conversion method, and the conventional boiling point of its hydrofining reaction effluent institute hydrocarbon-containifirst all is lower than 370 ℃.
The 3rd purpose of the present invention is to provide a kind of coal tar hydro-conversion method that is rich in the petroleum naphtha component, and the conventional boiling point of its hydrofining reaction effluent institute hydrocarbon-containifirst all is lower than 370 ℃.
The 4th purpose of the present invention is to provide the hydrogenating conversion process of a kind of high nitrogen-containing, high aromaticity content hydro carbons, and the conventional boiling point of its hydrofining reaction effluent institute hydrocarbon-containifirst all is lower than 370 ℃.
Summary of the invention
A kind of coal tar hydro-conversion method of the present invention is characterized in that comprising following steps:
1. in the hydrofining part, the coal tar hydro carbons is converted into the conventional boiling point of institute's hydrocarbon-containifirst and all is lower than 370 ℃ hydrofining reaction effluent and isolates at least one hydrofining diesel oil; At least a portion hydrofining diesel oil is as hydro-upgrading part material oil;
2. in the hydro-upgrading part, hydro-upgrading part material oil is converted into the hydro-upgrading reaction effluent and isolates hydro-upgrading diesel oil.
A kind of as mentioned above coal tar hydro-conversion method, its feature further is: when hydrofining partly had two or more hydrofining diesel oil, the hydrofining diesel oil that enters the hydro-upgrading part was low-cetane hydrofining diesel oil.
A kind of as mentioned above coal tar hydro-conversion method, its feature further is: hydro-upgrading diesel oil is compared with hydro-upgrading stock oil, and cetane value improves 4 units usually at least, preferably improves 8 units at least.
A kind of as mentioned above coal tar hydro-conversion method, its feature further is: hydro-upgrading diesel oil is compared with hydro-upgrading stock oil, and density reduces 20kg/m usually at least
3, preferably reduce 40kg/m at least
3
A kind of as mentioned above coal tar hydro-conversion method, its feature further is: the separate part of the separate part of hydrofining reaction effluent and hydro-upgrading reaction effluent, partly or entirely shared.
A kind of as mentioned above coal tar hydro-conversion method, its feature further is: the hydrofining reaction condition is: temperature is that 240～440 ℃, pressure are that 4.0～25.0MPa, Hydrobon catalyst volume space velocity are 0.1～4.0hr
-1, hydrogen to oil volume ratio is 400: 1～2500: 1; The hydro-upgrading reaction conditions is: temperature is that 280～460 ℃, pressure are that 4.0～25.0MPa, catalyst for hydro-upgrading volume space velocity are 0.1～3.0hr
-1, hydrogen to oil volume ratio is 300: 1～2500: 1.
A kind of as mentioned above coal tar hydro-conversion method, its feature further is: the hydrofining reaction condition is: temperature is that 300～420 ℃, pressure are that 6.0～15.0MPa, Hydrobon catalyst volume space velocity are 0.2～1.5hr
-1, hydrogen to oil volume ratio is 600: 1～1 500: 1; The hydro-upgrading reaction conditions is: temperature is that 320～440 ℃, pressure are that 6.0～15.0MPa, catalyst for hydro-upgrading volume space velocity are 0.2～1.5hr
-1, hydrogen to oil volume ratio is 400: 1～1500: 1.
A kind of as mentioned above coal tar hydro-conversion method, its feature further is: a part of hydro-upgrading diesel oil is done the oil circulation use of hydro-upgrading part material.
A kind of as mentioned above coal tar hydro-conversion method, its feature further is: hydro-upgrading part and hydrofining partial common, the circulation of part hydrofining diesel oil enters hydrofining reaction and partly carries out the secondary hydrogenation, and the round-robin hydrofining diesel oil is converted into hydro-upgrading petroleum naphtha and hydro-upgrading diesel oil; Hydrofining (hydro-upgrading) reaction conditions is: temperature is that 240～440 ℃, pressure are that 4.0～25.0MPa, Hydrobon catalyst volume space velocity are 0.1～4.0hr
-1, hydrogen to oil volume ratio is 400: 1～2500: 1.When separation hydrofining reaction effluent obtained two hydrofining diesel oils, a part of low-cetane hydrofining diesel oil circulation entered hydrofining reaction and partly carries out the secondary hydrogenation.
Embodiment
Below describe the present invention in detail.
Conventional boiling point of the present invention refers to the vapor-liquid equilibrium temperature of material under a barometric point.
Conventional gas hydrocarbon of the present invention refers to and is the gasiform hydro carbons under the normal condition, comprises methane, ethane, propane, butane.Conventional liq hydrocarbon of the present invention refers to the hydro carbons that is in a liquid state under the normal condition, comprises the hydro carbons that pentane and boiling point thereof are higher.
Proportion of the present invention unless stated otherwise, refers to the ratio of water-mass density under fluid density and normal pressure under normal pressure, the 15.6 ℃ of conditions, the 15.6 ℃ of conditions.
Petroleum naphtha of the present invention refers to conventional boiling point and is lower than 180 ℃ conventional liq hydrocarbon.
It is 180～375 ℃ hydro carbons that diesel component of the present invention or diesel oil distillate refer to conventional boiling point.
Impurity composition of the present invention refers to the hydrocracking thing of non-hydrocarbon component in the stock oil such as water, ammonia, hydrogen sulfide etc.
The composition of component of the present invention or concentration or content or yield value unless stated otherwise, are the weight basis value.
Coal tar hydro carbons of the present invention refers to the coal tar that is suitable for hydrotreatment, and the conventional boiling point of its hydrofining reaction effluent institute hydrocarbon-containifirst all is lower than 370 ℃.Because raw coal character and coking or gas-making process condition all change within the specific limits, the coal tar oil properties also changes within the specific limits.Coal tar oil properties of the present invention, organic oxygen level is generally 0.3～11%, especially be 3.5～10%, be 5～10% more particularly, proportion is generally 0.90～1.05, conventional boiling point is generally 60～390 ℃ and is generally 120～370 ℃, and metal content is that 5～30PPm, sulphur content are 0.15～0.9% usually, nitrogen content is 0.4～1.5%, common inorganic water-content is 0.2～5.0%.
Oxygen enrichment coal tar of the present invention, referring to organic oxygen level is higher than 2.5%, is higher than 4.0% coal tar especially, and its heavy constituent must just can be converted into diesel component through the hydro-upgrading process, and the conventional boiling point of its hydrofining reaction effluent institute hydrocarbon-containifirst all is lower than 370 ℃.
Wide fraction coal tar of the present invention, refer to and contain conventional boiling point and be higher than the coal tar that 300 ℃ of cuts and conventional boiling point are lower than 300 ℃ of cuts, and its heavy constituent must just can be converted into diesel component through the hydro-upgrading process, and the conventional boiling point of its hydrofining reaction effluent institute hydrocarbon-containifirst all is lower than 370 ℃.
Two-stage method hydrogenation of the present invention, the hydrotreatment process that refers to feedstock conversion and be the finished product comprises two hydrogenation reaction systems (hydrofining reaction system and hydro-upgrading reactive system) and two supporting reaction effluent separation systems (hydrofining reaction effluent separation system and hydro-upgrading reaction effluent separation system).Hydrofining generates oil content and heats up in a steamer the isolated a certain diesel oil of system (normally last running product) as the stock oil of hydro-upgrading reactive system, two hydrogenation reaction systems form overall serial flow on the stock oil flow process.
Below describe hydrofining part of the present invention in detail.
Coal tar raw material enters before the hydrofining part, carries out processed and filtration usually and takes off the solid particulate processing.When coal tar raw material character is better, can directly make the hydrofining raw material.
In the hydrofining part, the coal tar hydro carbons is converted into the conventional boiling point of its hydrofining reaction effluent institute hydrocarbon-containifirst and all is lower than 370 ℃ hydrofining reaction effluent, separates the hydrofining reaction effluent and obtains hydrofining petroleum naphtha and at least one hydrofining diesel oil;
In the hydrofining reaction part, under the Hydrobon catalyst existence condition, described coal tar and hydrogen are finished hydrofining reaction, generate a hydrofining reaction effluent of being made up of hydrogen, impurity component, conventional gas hydrocarbon, conventional liq hydrocarbon;
Hydrofining reaction of the present invention, be commonly referred to as the refining reaction process of the consumption hydrogen that coal tar takes place under hydrogen and appropriate catalyst existence condition, its minimum reaction depth should possess MIN industrial significance: be hydro-upgrading proper raw material oil partly is provided, should determine the requirement of feedstock property according to feed coal tar character and hydro-upgrading part catalyzer: generally this process is reduced to the living olefiant nitrogen content of hydrofining below the 1500PPm, is reduced to usually below the 800PPm, preferably is reduced to below the 400PPm; General this process is given birth to olefiant sulphur content with hydrofining and is reduced to below the 400PPm, is reduced to usually below the 300PPm, preferably is reduced to below the 200PPm; General this process to the carbon residue decreasing ratio of feed coal tar greater than 70%, usually greater than 90%, more preferably greater than 95%, to delay the knot charcoal speed of hydro-upgrading partial hydrogenation catalyzer, prolong the operational cycle of hydro-upgrading part catalyzer.
The hydrofining part, common operational condition: temperature is that 240～440 ℃, pressure are that 4.0～25.0MPa, Hydrobon catalyst volume space velocity are that 0.1～4.0hr-1, hydrogen to oil volume ratio are 400: 1～2500: 1; Suitable operational condition is: temperature is that 300～420 ℃, pressure are that 6.0～15.0MPa, Hydrobon catalyst volume space velocity are that 0.2～1.5hr-1, hydrogen to oil volume ratio are 600: 1～1500: 1.
Described hydrofining part, different because of the difference of coal tar raw material character (metal content, oxygen level, sulphur content, nitrogen content, aromaticity content, boiling range, proportion) and the hydrofining reaction degree of depth (hydrogenation deoxidation, hydrogenating desulfurization, hydrodenitrification, hydrogenation are saturated), the variation range of its operational condition is very wide, should determine according to concrete process condition.
Described hydrofining part, the Hydrobon catalyst of use comprises Hydrobon catalyst usually, and described Hydrobon catalyst can be the series combination of one or both or multiple catalyzer and load in mixture.Hydrobon catalyst, can be the coal tar hydrorefining special-purpose catalyst, also can be Hydrobon catalyst and combinations thereof such as the hydrogenating desulfurization agent used of the unifining process of suitable refining of petroleum diesel oil and/or wax oil, hydrodenitrification agent, removal of ccr by hydrotreating, hydrogenation aromatic hydrocarbons saturator.Because the coal tar metal content is higher usually, so use Hydrodemetalation catalyst (protective material) before Hydrobon catalyst.
Described hydrofining part, any additional sulphur can be added reactive moieties as required, with guarantee the necessary minimum concentration of hydrogen sulfide of reactive moieties such as 500PPm (v) or 1000PPm (v), to guarantee that the necessary hydrogen sulfide sectional pressure of catalyzer is not less than minimum must value.Described additional sulphur can be sulfide hydrogen maybe can be converted into hydrogen sulfide the coal tar hydrogenating conversion process is not had the material of undesirable action, such as hydrogen sulfide containing gas or oil product, or with the dithiocarbonic anhydride that is converted into hydrogen sulfide after high-temperature hydrogen contacts or Methyl disulfide etc.
Before the hydrofining reaction effluent enters hydrofining cold anticyclone separate part, in the hydrofining reaction effluent, inject washing water usually.Described hydrofining reaction effluent reduces temperature (generally being and the heat exchange of reactive moieties raw material) usually earlier, mixes with the washing water that add then to form water filling back end hydrogenation refining reaction effluent.Washing water are used for absorbing ammonia and issuable other impurity such as the hydrogenchloride etc. of hydrofining reaction effluent, and the aqueous solution behind the absorption ammonia must absorb the hydrogen sulfide in the hydrofining reaction effluent.
Described hydrofining cold anticyclone separate part comprises cooling, the separating step of water filling back end hydrogenation refining reaction effluent.At this, described water filling back end hydrogenation refining reaction effluent reduces temperature (using air-cooler and or watercooler usually) earlier usually to about 30～70 ℃, best 30～60 ℃.
At hydrofining cold anticyclone separate part, described flowing water back end hydrogenation refining reaction effluent gas delivery is: the cold high score gas of a hydrofining gas of mainly being made up of hydrogen on volume, the cold high score fluid of hydrofining body, the main cold high score water of a hydrofining liquid that be made up of water and that be dissolved with hydrogen sulfide, ammonia of mainly being made up of conventional liq hydrocarbon and dissolved hydrogen.The cold high score water of described hydrofining liquid, wherein the content of ammonia is generally 1～15% (w), is preferably 3～8% (w).A purpose annotating washing water is ammonia and the hydrogen sulfide that absorbs in the hydrofining reaction effluent, prevents that the hydrofining reaction effluent process that cools from forming sulphur hydrogenation ammonia or heat exchanger channel is stopped up in the crystallization of many sulphur ammonia, increases system pressure drop.
The injection rate of described washing water, should determine according to following principle: on the one hand, washing water are divided into vapour phase water and liquid phase water after injecting the hydrofining reaction effluent, the liquid phase water yield must be greater than zero, be preferably the washing water total amount 30% or more; On the one hand, washing water are used for absorbing the ammonia of hydrotreated product, prevent that the ammonia concentration of the cold high score gas of hydrofining is too high again, reduce catalyst activity, usually the ammonia volumetric concentration of the cold high score gas of hydrofining is low more good more, generally is not more than 200PPm and (v), preferably is not more than 50PPm (v).
Described hydrofining cold anticyclone separate part, its separator operation pressure falls for the hydrofining partial pressure deducts true pressure, the difference of hydrofining cold anticyclone separate part working pressure and hydrofining partial pressure should not be crossed lowly or too high, is generally 0.5～1.2MPa.
The cold high score gas of described hydrofining gas, its density of hydrogen value, should not be low excessively (causing the device working pressure to rise), generally should be not less than 70% and (v), should be not less than 80% and (v), preferably be not less than 85% (v).
As previously mentioned at least a portion, be generally 85～100% the cold high score gas of described hydrofining gas and return hydrofining and partly form circulating hydrogen, so that necessary amounts of hydrogen of hydrofining part and hydrogen concentration to be provided; In order to improve plant investment efficient, must guarantee that hydrofining recycle hydrogen concentration is not less than aforesaid low limit value, for this reason, distribute according to concrete feedstock property, reaction conditions, product, can get rid of the cold high score gas of a part of described hydrofining gas (hereinafter to be referred as the cold high score gas discharging of hydrofining gas) to get rid of methane, the ethane that reaction produces.For the cold high score gas discharging of hydrofining gas, can adopt conventional membrane separation process or pressure swing adsorption technique or oil wash technology to realize that hydrogen separates with non-hydrogen gaseous fraction, and the hydrogen that reclaims is used as new hydrogen.
The new hydrogen of hydrofining enters the hydrofining part to replenish the hydrogen that hydrofining partly consumes, and the new hydrogen hydrogen concentration of hydrofining is high more good more, generally should not be lower than 95% and (v), preferably be not less than 99% (v).
Before the hydrofining cold anticyclone separate part thermal high separate part can be set.
The separating of oil part of the cold high score of hydrofining described herein, be meant that the cold high score fluid of hydrofining body is separated into the step of narrow fraction products such as hydrofining petroleum naphtha and at least one hydrofining diesel oil, its narrow fraction product can be used as the use of hydro-upgrading part material oil such as mainly being higher than 200 ℃ component by conventional boiling point or mainly being higher than 250 ℃ component or mainly being higher than the hydrofining diesel oil that 300 ℃ component is formed by conventional boiling point by conventional boiling point.At this, the cold high score oil of described hydrofining at first reduces pressure, pressure is reduced to 0.5～4.0MPa formation gas, the logistics of liquid mixed phase usually, then through separation with or fractionated process finish and separate, be separated into gas, liquefied gas, naphtha fraction and at least one diesel oil distillate etc. usually.
The objective of the invention is to: for the hydrogenation catalyst performance of giving full play to hydro-upgrading part and or avoid the excessive hydrogenation of hydrofining petroleum naphtha component or hydrofining solar oil component, generate the oil separating part in hydrofining the hydrofining reaction effluent is separated to deviate from ammonia and/or water and/or lighting end, obtain the stock oil of hydrofining diesel oil as the hydro-upgrading part.When hydrofining partly had two or more hydrofining diesel oil, hydro-upgrading stock oil was low-cetane hydrofining diesel oil.
Below describe hydro-upgrading part of the present invention in detail.
In the hydro-upgrading part, under the catalyst for hydro-upgrading existence condition, hydro-upgrading stock oil and hydrogen are finished the hydro-upgrading reaction, generate a hydro-upgrading reaction effluent of being made up of hydrogen, impurity component, conventional gas hydrocarbon, conventional liq hydrocarbon.
The hydro-upgrading part, common operational condition is: temperature is that 280～460 ℃, pressure are that 4.0～25.0MPa, catalyst for hydro-upgrading volume space velocity are 0.1～3.0hr
-1, hydrogen to oil volume ratio is 300: 1～2500: 1; Suitable operational condition is: temperature is that 320～440 ℃, pressure are that 6.0～1 5.0MPa, catalyst for hydro-upgrading volume space velocity are 0.2～1.5hr
-1, hydrogen to oil volume ratio is 400: 1～1500: 1.
Described hydro-upgrading part, different because of the hydro-upgrading reaction depth of the difference of its feedstock property (nitrogen content, aromaticity content) and expection, the variation range of its operational condition is very wide, should determine according to concrete process condition.
The hydro-upgrading of hydro-upgrading part of the present invention reacts a speech, refer under hydrogen and appropriate catalyst existence condition, the reaction process (comprising cracking reaction usually) of the consumption hydrogen that hydro-upgrading part material fry dried food ingredients is given birth to, its minimum reaction depth should possess MIN industrial significance: such as the diesel oil distillate of producing expection character, should be according to hydro-upgrading part material oil nature, expection diesel oil distillate character is determined with the catalyst for hydro-upgrading performance: hydro-upgrading diesel oil is compared with hydro-upgrading stock oil, and cetane value improves 4 units usually at least, preferably improve 8 units at least; Hydro-upgrading diesel oil is compared with hydro-upgrading stock oil, and density reduces 20kg/m usually at least
3, preferably reduce 40kg/m at least
3
Hydro-upgrading part as mentioned above, normally used hydrogenation catalyst comprise have the saturated function of aromatic hydrocarbons and or the catalyzer of hydrocracking function, catalyst for hydro-upgrading can be the series combination of one or both or multiple catalyzer and load in mixture.Catalyst for hydro-upgrading can be catalyst for hydro-upgrading and the combination thereof that the hydro-upgrading process of suitable petroleum refining process diesel oil (comprising poor ignition quality fuel) and/or wax oil is used.
Hydro-upgrading part as mentioned above, can select amorphous (sial) hydrocracking catalyst of not fusion molecular sieve or amorphous (sial) hydrocracking catalyst of a small amount of fusion molecular sieve for use, to strengthen adaptive faculty as far as possible, improve the diesel component productive rate to organic nitrogen compound in the raw material.Hydro-upgrading part also can be used the dual-functional hydrogenation modifying catalyst with the saturated and open loop of aromatic hydrocarbons, can also use the catalyzer with the saturated function of hydrogenation.
According to the present invention, the separation steps of hydro-upgrading reaction effluent may comprise the hydro-upgrading cold anticyclone separate part of the refrigerated separation process of independently finishing the hydro-upgrading reaction effluent, also may comprise water filling and wash ammonia step, thermal high separating step.
At hydro-upgrading cold anticyclone separating step, the hydro-upgrading reaction effluent enters service temperature and is generally 30～60 ℃ hydro-upgrading cold high pressure separator and is separated into: the cold high score gas of a hydro-upgrading gas of mainly being made up of hydrogen on volume, the main cold high score fluid of a hydro-upgrading body of being made up of conventional gas hydrocarbon, conventional liq hydrocarbon and dissolved hydrogen.Described hydro-upgrading cold anticyclone separate part, its working pressure falls for the hydro-upgrading partial pressure deducts true pressure, the difference of hydro-upgrading cold anticyclone separate part working pressure and hydro-upgrading partial pressure should not be crossed lowly or too high, is generally 0.5～1.2MPa.The cold high score fluid of hydro-upgrading body is isolated diesel oil distillate at its separate part: at this, the cold high score oil of hydro-upgrading at first reduces pressure, pressure is reduced to 0.5～4.0MPa formation gas, the logistics of liquid mixed phase usually, then through separation with or fractionated process finish and separate, be separated into products such as gas, liquefied gas, naphtha fraction, diesel oil distillate usually.
The cold high score gas of described hydro-upgrading gas, its density of hydrogen value, should not be low excessively (causing the device working pressure to rise), generally should be not less than 70% and (v), should be not less than 80% and (v), preferably be not less than 85% (v).
As previously mentioned at least a portion, be generally 85～100% the cold high score gas of described hydro-upgrading gas and return hydro-upgrading and partly form circulating hydrogen, so that necessary amounts of hydrogen of hydro-upgrading part and hydrogen concentration to be provided; In order to improve plant investment efficient, must guarantee that hydro-upgrading recycle hydrogen concentration is not less than aforesaid low limit value, for this reason, distribute according to concrete feedstock property, reaction conditions, product, can get rid of the cold high score gas of a part of described hydro-upgrading gas (hereinafter to be referred as the cold high score gas discharging of hydro-upgrading gas) to get rid of methane, the ethane that reaction produces.Discharge gas for the cold high score gas of hydro-upgrading, can adopt conventional membrane separation process or pressure swing adsorption technique or oil wash technology to realize hydrogen-non-hydrogen gaseous fraction separation, and the hydrogen that reclaims is used as new hydrogen.
In order to simplify flow process and to reduce construction investment, can be with the separate part of hydrofining reaction effluent and the separate part of hydro-upgrading reaction effluent, partial common at least.The cold anticyclone separate part of hydro-upgrading reaction effluent and the cold anticyclone separate part of hydrofining reaction effluent merge: the hydro-upgrading reaction effluent enters hydrofining cold anticyclone separate part, contacts and finish the sepn process that hydro-upgrading partly generates oil and hydrogen with the hydrofining reaction effluent.In above-mentioned flow process, hydrofining generates oil and hydro-upgrading generation oil mixes, and therefore, is particularly suitable for the darker situation of the hydrofining partial hydrogenation degree of depth.
The new hydrogen of hydro-upgrading enters the hydro-upgrading part to replenish the hydrogen that the hydro-upgrading process consumes, and the new hydrogen hydrogen concentration of hydro-upgrading is high more good more, generally should not be lower than 95% and (v), preferably be not less than 99% (v).
In order to implement the present invention, before hydro-upgrading cold anticyclone separate part, can increase hydro-upgrading thermal high separating step, in this flow process, the hydro-upgrading reaction effluent is introduced into service temperature and is generally 150～250 ℃, is preferably 180～230 ℃ hydro-upgrading thermal high separating step and is separated into: the hot high score gas of a hydro-upgrading gas of mainly being made up of hydrogen, impurity component, conventional gas hydrocarbon on volume, the main hot high score fluid of a hydro-upgrading body of being made up of conventional liq hydrocarbon and dissolved hydrogen.The hot high score gas of hydro-upgrading gas enters hydro-upgrading cold anticyclone separate part.The hot high score fluid of hydro-upgrading body is isolated diesel oil distillate at the hot high score fluid of hydro-upgrading body separate part (comprise and separate and or fractionated process).The hot high score fluid of hydro-upgrading body separate part and the cold high score fluid of hydro-upgrading body separate part can partial commons or all shared.
In order to implement the present invention, the hot high score gas of hydro-upgrading gas can be introduced the hydrofining cold anticyclone separate part of hydrofining reaction effluent, in the hope of simplifying flow process and reducing construction investment.In this flow process, hydrofining generates oil and partial hydrogenation upgrading generation oil mixes, and therefore, is particularly suitable for the darker situation of the hydrofining partial hydrogenation degree of depth.
In order to implement the present invention, the hot high score gas of hydro-upgrading gas can be introduced the hydrofining reaction part.In this flow process, hydrofining generates oil and hydro-upgrading generation oil mixes, and therefore, is particularly suitable for the darker situation of the hydrofining reaction partial hydrogenation degree of depth.Simultaneously, the hot high score gas of hydro-upgrading gas by second stage employ, can reduce the recycle hydrogen total amount through the hydrofining part significantly, can reduce investment of recycle hydrogen system and energy consumption significantly.When hydrofining is partly used a plurality of reactor, the hot high score gas of hydro-upgrading can enter arbitrary reactor inlet, or enter hydrofining part and contact with its beds with any other effective means, can be used as the cold hydrogen of hydrofining part uses, can obtain and reduce the circulating hydrogen total amount, reduce recycle hydrogen working cycle heat-energy losses (heat-energy losses of recycle hydrogen in the temperature-fall period of air cooler and water cooler) and reduce (the cooling of hydro-upgrading hot high score gas gas and hydrofining reaction effluent gas of high top pressure operation step, the ammonia step is washed in water filling, the gas-oil separation step is merged, and the additional sulphur of hydro-upgrading part is in hydrofining part second stage employ) unusual effect.
In order to implement the present invention, all new hydrogen can be introduced hydrofining part or hydro-upgrading part.
Metal, oxygen, sulphur, the nitrogen of the typical coal tar hydrogenating conversion process of the present invention in can effective elimination coal tar, make wherein saturated, the cracking of at least a portion polynuclear compound, oil property is improved significantly, and the naphtha fraction product can be used as high-quality catalytic reforming raw material component, the diesel oil distillate product can be used as fine-quality diesel oil blending component.
Coal tar hydro-conversion method of the present invention can be done the oil circulation use of hydro-upgrading part material with a part of hydro-upgrading diesel oil, with further raising hydro-upgrading diesel quality (as improving cetane value).
A kind of special flow formula of coal tar hydro-conversion method of the present invention is: hydro-upgrading part and hydrofining partial common, part hydrofining diesel oil (usually with hydrofining fresh feed oil in the diesel component weight ratio be 0.05～0.70) circulating enters hydrofining reaction and partly carries out the secondary hydrogenation, form diesel cycle hydrogenation flow process, the round-robin hydrofining diesel oil is converted into hydro-upgrading petroleum naphtha and hydro-upgrading diesel oil; Hydrofining (hydro-upgrading) reaction conditions is: temperature is that 240～440 ℃, pressure are that 4.0～25.0MPa, Hydrobon catalyst volume space velocity are 0.1～4.0hr
-1, hydrogen to oil volume ratio is 400: 1～2500: 1.When separation hydrofining reaction effluent obtained two hydrofining diesel oils, a part of low-cetane hydrofining diesel oil circulation entered hydrofining reaction and partly carries out the secondary hydrogenation.
Embodiment one
Coal tar raw material A character sees Table 1, and the catalyzer composition sees Table 2.From operational condition and diesel product property list (table 3) as can be seen: all hydrofining diesel oils are behind hydro-upgrading, and cetane value improves 7 units.
Table 1 coal tar raw material A character
| Project | Numerical value |
| The raw material numbering | Raw material A |
| Density (20 ℃), g.cm -3 | ????0.951 |
| Boiling range, ℃ | |
| IBP/50％ | ????76/211 |
| 95％/EBP | ????351/390 |
| S，m％ | ????1.11 |
| N，m％ | ????0.92 |
| Existent gum, mg/100ml | Do not blow and do |
| Iodine number, gI/100g | ????29.5 |
| 10% carbon residue, m% | ????11.5 |
Table 2 catalyzer is formed
| The catalyzer numbering | Catalyst A 1 | Catalyst A 2 | Catalyst A 3 |
| The catalyzer classification | Protective material | Hydrofining | Saturated and the open loop of aromatic hydrocarbons |
| Chemical constitution, m% WO 3????MoO 3The NiO molecular sieve | ??6.0～8.0 ??1.5～2.5 | ??17～21 ??8～10 ??3.5～5.5 | 16～20 6～9 21～25 |
| Carrier | ??γ-Al 2O 3 | Amorphous silicon aluminium+Al 2O 3+SSY | |
| Auxiliary agent, wt% | ??P 2O 5：3～4.5 | F：3～4 |
Table 3 operational condition and diesel product character
| Project | Embodiment one |
| The hydrofining part | |
| Reaction pressure, MPa | ????14～15 |
| Temperature of reaction, ℃ | ????360～370 |
| Catalyst A 2 volume space velocities, h -1 | ????0.4～0.5 |
| The reactor inlet hydrogen-oil ratio, m 3n/m 3 | ????1000～1200 |
| The hydrofining diesel oil cetane index | ????～29 |
| Hydrofining diesel oil is done, ℃ | ????＜370 |
| The hydro-upgrading part | |
| Reaction pressure, MPa | ????14～15 |
| Temperature of reaction, ℃ | ????360～375 |
| Catalyst A 3 volume space velocities, h -1 | ????0.4～0.6 |
| The reactor inlet hydrogen-oil ratio, m 3n/m 3 | ????600～800 |
| Hydro-upgrading diesel oil cetane index | ????＞36 |
Embodiment two
Coal tar raw material A (character sees Table 1), the catalyzer composition sees Table 4.Hydrofining Primary Catalysts bed be catalyst B 21 and catalyst B 22 by volume half and half, load in mixture bed after mixing.
From operational condition and diesel product property list (table 5) as can be seen: hydrofining diesel oil is behind hydro-upgrading, and cetane value improves 7.5 units, and density reduces 45kg/m
3
Table 4 catalyzer is formed
| The catalyzer numbering | Catalyst B 1 | Catalyst B 21 | Catalyst B 22 | Catalyst B 3 |
| The catalyzer classification | Protective material | Hydrofining | Hydrofining | Hydrocracking |
| Chemical constitution, m% WO 3??MoO 3The NiO molecular sieve | ??6.0～8.0 ??1.5～2.5 | ??17～21 ??8～10 ??3.5～5.5 | ??23～25 ??3.5～5.0 | 22～25 5.5～7.5 trace |
| Carrier | ??γ-Al 2O 3 | Modification on Al 2O 3 | Amorphous silicon aluminium | |
| Auxiliary agent, wt% | ??P 2O 5：3～4.5 | ??P：1～2 |
Table 5 operational condition and diesel product property list
| Project | Embodiment two |
| The hydrofining part | |
| Reaction pressure, MPa | ????14～15 |
| Temperature of reaction, ℃ | ????360～370 |
| The catalyst for refining volume space velocity, h -1 | ????0.4～0.5 |
| The reactor inlet hydrogen-oil ratio, m 3n/m 3 | ????1000～1200 |
| The hydrofining diesel oil cetane index | ????～30.5 |
| Hydrofining diesel oil is done, ℃ | ????＜370 |
| Diesel product quantity | ????2 |
| The hydrocracking raw material diesel boiling range, ℃ | ????230～370 |
| The hydrocracking part | |
| Reaction pressure, MPa | ????14～15 |
| Temperature of reaction, ℃ | ????360～375 |
| The hydrocracking catalyst volume space velocity, h -1 | ????0.4～0.6 |
| The reactor inlet hydrogen-oil ratio, m 3n/m 3 | ????600～800 |
| Hydro-upgrading diesel oil cetane index | ????＞38 |
| Hydro-upgrading diesel oil density, kg/m 3 | Than hydrocracking raw material oil density low 45 |
Embodiment three
Present embodiment adopts the flow process of hydro-upgrading part and hydrofining partial common, a part of hydrofining diesel oil (with diesel component weight ratio in the hydrofining fresh feed oil be 0.5) circulation enters hydrofining reaction and partly carries out the secondary hydrogenation.Coal tar raw material B character sees Table 6, and the catalyzer composition sees Table 7.
From operational condition and diesel product property list (table 8) as can be seen: compare with comparative example, embodiment three schemes 1 diesel product cetane value is high more than 2.2, and scheme 2 diesel product cetane value are high more than 3.1.
Table 6 coal tar raw material B character
| Project | Numerical value |
| Raw material numbering oil property: density (20 ℃), g/cm 3Boiling range ASTM D86, ℃ initial boiling point/50%/final boiling point nitrogen content, ppm sulphur content, ppm acidity, mgKOH/100ml cetane index (ASTM D4737) | Raw material B 0.925 6,0/2,46/,382 7,152 4,251 22.1 20 |
Table 7 catalyzer is formed
| The catalyzer numbering | Catalyzer C1 | Catalyzer C2 |
| The catalyzer classification | Protective material | Hydrofining (hydro-upgrading) |
| Chemical constitution, m% WO 3??MoO 3??NiO | ????6.0～8.0 ????1.5～2.5 | ????17～21 ????8～10 ????3.5～5.5 |
| Carrier | ????γ-Al 2O 3 | |
| Auxiliary agent P 2O 5，wt％ | ????3～4.5 | |
| Specific surface area, m 2/g | ????～175 | ????≮120 |
| Pore volume, ml/g | ????～0.55 | ????～0.30 |
Table 8 operational condition and diesel product character
| Project | Comparative example | Embodiment three schemes 1 | Embodiment three schemes 2 |
| Reaction pressure, MPa | ??8.0 | ??8.0 | ??8.0 |
| Temperature of reaction, ℃ | ??375 | ??375 | ??375 |
| Catalyzer C2 volume space velocity, h -1 | ??0.8 | ??0.8 | ??0.8 |
| The reactor inlet hydrogen-oil ratio, m 3n/m 3 | ??800 | ??800 | ??800 |
| Diesel product quantity | ??1 | ??2 | |
| The circulation diesel boiling range, ℃ | No circulation diesel oil | ??180～370 | ??240～370 |
| Circulation diesel oil is to diesel component weight ratio in the stock oil | No circulation diesel oil | ??0.5 | ??0.5 |
| The diesel product cetane index | ??35.0 | ??＞37.2 | ??＞38.1 |
Claims (12)
1, a kind of coal tar hydro-conversion method is characterized in that comprising following steps:
1. in the hydrofining part, the coal tar hydro carbons is converted into the conventional boiling point of institute's hydrocarbon-containifirst and all is lower than 370 ℃ hydrofining reaction effluent and isolates at least one hydrofining diesel oil; At least a portion hydrofining diesel oil is as hydro-upgrading part material oil;
2. in the hydro-upgrading part, hydro-upgrading part material oil is converted into the hydro-upgrading reaction effluent and isolates hydro-upgrading diesel oil.
2, according to the described method of claim 1, it is characterized in that: when hydrofining partly had two or more hydrofining diesel oil, the hydrofining diesel oil that enters the hydro-upgrading part was low-cetane hydrofining diesel oil.
3, according to the described method of claim 1, it is characterized in that: hydro-upgrading diesel oil is compared with hydro-upgrading stock oil, and cetane value improves 4 units at least.
4, according to the described method of claim 1, it is characterized in that: hydro-upgrading diesel oil is compared with hydro-upgrading stock oil, and cetane value improves 8 units at least.
5, according to the described method of claim 1, it is characterized in that: hydro-upgrading diesel oil is compared with hydro-upgrading stock oil, and density reduces 20kg/m at least
3
6, according to the described method of claim 1, it is characterized in that: hydro-upgrading diesel oil is compared with hydro-upgrading stock oil, and density reduces 40kg/m at least
3
7, according to the described method of claim 1, it is characterized in that: the separate part of the separate part of hydrofining reaction effluent and hydro-upgrading reaction effluent, partial common at least.
8, according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 described methods, it is characterized in that: the hydrofining reaction condition is: temperature is that 240～440 ℃, pressure are that 4.0～25.0MPa, Hydrobon catalyst volume space velocity are 0.1～4.0hr
-1, hydrogen to oil volume ratio is 400: 1～2500: 1; The hydro-upgrading reaction conditions is: temperature is that 280～460 ℃, pressure are that 4.0～25.0MPa, catalyst for hydro-upgrading volume space velocity are 0.1～3.0hr
-1, hydrogen to oil volume ratio is 300: 1～2500: 1.
9, described according to Claim 8 method, it is characterized in that: the hydrofining reaction condition is: temperature is that 300～420 ℃, pressure are that 6.0～15.0MPa, Hydrobon catalyst volume space velocity are 0.2～1.5hr
-1, hydrogen to oil volume ratio is 600: 1～1500: 1; The hydro-upgrading reaction conditions is: temperature is that 320～440 ℃, pressure are that 6.0～15.0MPa, catalyst for hydro-upgrading volume space velocity are 0.2～1.5hr
-1, hydrogen to oil volume ratio is 400: 1～1500: 1.
10, according to claim 1 or 2 or 3 or 4 or 5 or 6 described methods, it is characterized in that: hydro-upgrading part and hydrofining partial common, a part of hydrofining diesel oil circulation enters hydrofining reaction and partly carries out the secondary hydrogenation.The hydrofining reaction condition is: temperature is that 240～440 ℃, pressure are that 4.0～25.0MPa, Hydrobon catalyst volume space velocity are 0.1～4.0hr
-1, hydrogen to oil volume ratio is 400: 1～2500: 1.
11, according to the described method of claim 10, it is characterized in that: separate the hydrofining reaction effluent and obtain two hydrofining diesel oils, a part of low-cetane hydrofining diesel oil circulation enters hydrofining reaction and partly carries out the secondary hydrogenation.
12, described according to Claim 8 method, a part of hydro-upgrading diesel oil is done the oil circulation use of hydro-upgrading part material.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104531212A (en) * | 2014-12-05 | 2015-04-22 | 何巨堂 | High aromatic hydrocarbon hydrogenation upgrading method by utilizing refined diesel component hydrogenation upgrading reaction process |
| CN105018141A (en) * | 2014-04-30 | 2015-11-04 | 何巨堂 | High-aromatic-hydrocarbon hydro-upgrading method used in upgrading process after naphtha components are used |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105018141A (en) * | 2014-04-30 | 2015-11-04 | 何巨堂 | High-aromatic-hydrocarbon hydro-upgrading method used in upgrading process after naphtha components are used |
| CN104531212A (en) * | 2014-12-05 | 2015-04-22 | 何巨堂 | High aromatic hydrocarbon hydrogenation upgrading method by utilizing refined diesel component hydrogenation upgrading reaction process |
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