CN101067095A - Method of recovering heat in hydrocarbon hydrogenating conversion process - Google Patents
Method of recovering heat in hydrocarbon hydrogenating conversion process Download PDFInfo
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- CN101067095A CN101067095A CNA2006101535199A CN200610153519A CN101067095A CN 101067095 A CN101067095 A CN 101067095A CN A2006101535199 A CNA2006101535199 A CN A2006101535199A CN 200610153519 A CN200610153519 A CN 200610153519A CN 101067095 A CN101067095 A CN 101067095A
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Abstract
The present invention relates to method of recovering heat in hydrocarbon hydrogenating conversion process. The low temperature heat absorbing oil and the reaction resultant are heat exchanged to form high temperature heat absorbing oil, which enters to the bottom of the fractionating tower so as to mix with the liquid phase material flow inside the fractionating tower before being shunt into low temperature heat absorbing oil for reuse. The process is especially suitable for hydrogenating conversion of coal tar, and has the advantages of high heat utilizing rate, reduced hydrogen circulating system scale and reduced the scale of reboiling furnace in the fractionating tower. In addition, the heat absorbing oil heat exchanger may be used as the heater for starting the reactor or sulfurizing to reduce heat load of the heating furnace.
Description
Technical field
The present invention relates to a kind of high hydrogen consumption method of recovering heat in hydrocarbon hydrogenating conversion process; Say especially, the present invention relates to a kind of coal tar hydrogenating conversion process heat recovery method.
Background technology
As everyone knows, the hydrocarbons raw oil hydroconversion process is the conversion process of hydrocarbon feed under catalyzer and hydrogen existence condition, is widely used in the oil product upgrading.The high-pressure separator hydrocarbon liquid that hydroconversion process produces is by the conventional liq hydrocarbon and be dissolved in wherein conventional gas hydrocarbon and non-hydrocarbon component such as H
2S, H
2O, NH
3, H
2Deng composition.Usually, described high-pressure separator hydrocarbon liquid at first enters in the light pressure separator, is that 0.5～4.0MPa, temperature are under 35～60 ℃ of conditions at pressure, is separated into mainly by H
2And C
1, C
2Low minute gas gas that hydrocarbon is formed and mainly by C
3And low minute petroleum hydrocarbon liquid of above hydrocarbon composition.Then, the low oil that divides enters stabilizer tower (debutanizing tower or depentanizer or dehexanizing column or de-hydrogen sulfide column etc.), is under the operational condition of 0.8～2.3MPa at pressure, is separated into and is rich in C
3, C
4The stable overhead gas of hydrocarbon, mainly by C
3, C
4The stable cat head liquid hydrocarbon that hydrocarbon is formed and mainly by C
5And oil at the bottom of the stabilizer tower of above hydrocarbon composition.Oil further is separated into close-cut fraction product such as petroleum naphtha, diesel oil, wax oil etc. at the bottom of the stabilizer tower.About method of recovering heat in hydrocarbon hydrogenating conversion process, the intermediate reaction effluent cooling process is to use cold hydrogen or cold oil directly to cool off, cold hydrogen or cold oil change high-temperature hydrogen or high temperature oil (oil gas) into, carry out heat recuperation as the part of end reaction effluent; End reaction effluent heat recovery method is heating raw oil, hydrogen, low oil and the generation steam of dividing.The shortcoming of above-mentioned heat recovery method is:
1. intermediate reaction effluent heat recovery method uses cold hydrogen or cold oil, increase cold hydrogen recycle system scale or increased the cold oil recycle system, increased investment, simultaneously high potential temperature heat energy (such as 410～370 ℃ of heat energy) is converted into lower temperature position heat energy (such as 410～50 ℃ of heat energy), wherein 180～50 ℃ of heat energy can't reclaim (usually with air cooler or water cooler cooling), wherein 410～180 ℃ of energy recovery processes use interchanger directly to use interchanger to compare with the intermediate reaction effluent, because potential temperature reduces significantly, the high pressure heat exchanger investment increases greatly;
2. end reaction effluent heat recovery method is that heating raw oil, hydrogen, low oil and the superfluous heat energy of dividing are used to take place steam, is lower than the liquid that heavily boils at the bottom of direct heating process stream or the direct heating separation column but the steam thermal energy utilization ratio takes place.
For the hydroconversion process of high hydrogen consumption hydrocarbon hydrogenating conversion process such as coal tar or shale oil, because the hydrogen consumption is high, the exothermic heat of reaction amount is big, and there is excessive heat energy in effluent in the middle of the reaction; Because of easily reactive component is many in the raw material, reacting initial temperature is very low again, and the fuel oil preheating temperature is low, also has excessive heat energy in the end reaction effluent, and the shortcoming of conventional hydroconversion process heat recovery method is more obvious.And the objective of the invention is to propose a kind of coal tar hydrogenating conversion process heat recovery method.
Summary of the invention
A kind of method of recovering heat in hydrocarbon hydrogenating conversion process of the present invention is characterized in that comprising following steps:
1. the heat exchange of reaction effluent and low temperature heat-obtaining oil forms low-temp reaction effluent and high temperature heat-obtaining oil;
2. high temperature heat-obtaining oil enters separation column bottom, after liquid phase stream mixes in the separation column, splits into low temperature heat-obtaining oil again and returns step and 1. recycle.
According to the present invention, described reaction effluent can be the intermediate reaction effluent, heat exchange this moment effect is to save cold hydrogen consumption, reduces the recycle hydrogen system scale, reduces the investment of recycle hydrogen system, and saving simultaneously divides the furnace fuel consumption, reduces and divide furnace scale and investment.
According to the present invention, described reaction effluent can be the end reaction effluent, and heat exchange this moment effect is to reclaim end reaction effluent heat energy, saves simultaneously and divides furnace fuel consumption, reduction to divide furnace scale and investment.
According to the present invention, described high temperature heat-obtaining oil can enter the branch furnace and further heat before returning the separation column bottom, and the total amount to reduce heat-obtaining oil and to divide furnace heavily to boil the liquid internal circulating load reduces the recycle pump energy consumption, reduces recycle system investment.
According to the present invention, in described heat-obtaining oil-circulation process, can use the logistics of interchanger heating process, steam takes place, hot water etc. takes place, also can use air cooler to reduce the heat-obtaining oil temperature and be used to discharge the heat of heat-obtaining oil in the surplus of reactive moieties absorption, be beneficial to and reduce follow-up high pressure heat exchanger material rate, reduce investment outlay.
According to the present invention, its operational condition is: the reaction effluent temperature is 300～480 ℃ and is preferably 380～440 ℃ that low temperature heat-obtaining oil temperature is 150～380 ℃ and is preferably 280～320 ℃; The temperature reduction is preferably 30～70 ℃ for 10～100 ℃ after the reaction effluent heat exchange.Temperature after the heat exchange of heat-obtaining oil can be by regulating the oil circulation amount control of heat-obtaining, the temperature after the heat exchange of heat-obtaining oil is general raise 30～150 ℃, should raise 50～90 ℃.
According to the present invention, reaction effluent is coal tar hydrogenating conversion reaction effluent or hydrogenation of shale oil conversion reaction effluent.
Description of drawings
Feed coal tar enters in the first reactive moieties reactor 3 through pipeline 1, hydrogen enters in the first reactive moieties reactor 3 through pipeline 2, the first reactive moieties reaction effluent enters in the second reactive moieties lead reactor 5 through managing 4, the second reactive moieties intermediate reaction effluent enters interchanger 7 and is cooled to the second reactive moieties low temperature intermediate reaction effluent and enters in the rearmounted reactor 9 of second reactive moieties through pipeline 8 through managing 6, the end reaction effluent enters that interchanger 11 cools and enters in the high-pressure separator 13 through pipeline 12 through managing 10, high score gas leaves high-pressure separator 13 tops and returns reactive moieties use after circulating hydrogen compressor boosts through managing 14, and high score oil leaves high-pressure separator 13 bottoms and removes light pressure separator through managing 15.
Low temperature heat-obtaining oil enters interchanger 7 and heats up with the heat exchange of intermediate reaction effluent, high temperature heat-obtaining oil enters separation column 23 bottoms through pipeline 22, after liquid phase stream mixes in the separation column, through pipeline 24, through pump 25, through pipeline 26, split into low temperature heat-obtaining oil and return interchanger 7 through pipeline 21 and recycle, the separation column bottoms is discharged through pipeline 30.Represented reboiler furnace flow process at the bottom of the fractionation Tata among the figure simultaneously, the liquid that heavily boils enters process furnace 28 heating through pipeline 27, and the thermogravimetric liquid that boils enters the separation column bottom through pipeline 29.
Represented simultaneously among the figure that low temperature heat-obtaining oil enters interchanger 11 and end reaction effluent heat exchange intensification, high temperature heat-obtaining oil enter separation column 23 bottoms through pipeline 222 situation through pipeline 211.
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 200 ℃ conventional liq hydrocarbon.
It is 200～375 ℃ 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 of the present invention refers to the coal tar that is suitable for hydrotreatment, 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 0.92～1.25, conventional boiling point is generally 60～530 ℃ and is generally 120～510 ℃, and metal content is that 5～80PPm, sulphur content are 0.4～0.8% usually, nitrogen content is 0.6～1.4%, common inorganic water-content is 0.2～5.0%.Before coal tar enters hydrogenator, general through dehydration and filtration treatment.
Hydrotreating catalyst of the present invention, refer to stock oil and touch the various hydrogenation catalysts that Hydrodemetalation catalyst touches later in hydrogenation process, the coal tar hydrogenating treating processes generally must be provided with first reactive moieties of using Hydrodemetalation catalyst and second reactive moieties of using hydrotreating catalyst.
Coal tar contain more under the mitigation condition the easily component of reaction such as metal ion, organic oxygen, rudimentary organosulfur, unsaturated hydrocarbons etc., therefore, hydrocracking part of the present invention refers to the hydrocracking part of using Hydrodemetalation catalyst and minimum a kind of hydrotreating catalyst (being generally Hydrobon catalyst).
According to the present invention, in first reactive moieties, under the Hydrodemetalation catalyst existence condition, described coal tar and hydrogen carry out hydrogenation reaction, generate first reaction effluent of being made up of hydrogen, impurity component, conventional gas hydrocarbon, conventional liq hydrocarbon; Based on the purpose of first reactive moieties is to remove metal, remove the organic oxygen of part (such as organic phenol) and to the easy hydrogenation of reactive component of part, therefore the reaction conditions of first reactive moieties is than the mitigation of the second reactive moieties reaction conditions.According to the present invention, the operational condition of first reactive moieties is generally: temperature is that 180～390 ℃, pressure are that 6.0～25.0MPa, catalyst for demetalation volume space velocity are 0.1～2.0hr
-1, hydrogen/stock oil volume ratio is 500: 1～3000: 1.According to the present invention, first reactive moieties operational condition preferably is preferably: temperature is that 200～370 ℃, pressure are that 10.0～20.0MPa, catalyst for demetalation volume space velocity are 0.2～0.5hr
-1, hydrogen/stock oil volume ratio is 1000: 1～2000: 1.
According to the present invention, in second reactive moieties, under hydrotreating catalyst (using the catalyzer that possesses the hydrofining function usually at least) existence condition, described first reaction effluent carries out hydrogenation reaction, generates second reaction effluent of being made up of hydrogen, impurity component, conventional gas hydrocarbon, conventional liq hydrocarbon; Common index request based on the modified fuel oil product of coal tar hydrogenating transform portion expection; must remove most of the nitrogen, remove most of sulphur, reduction aromatic hydrocarbons degree, improve cetane value, reduce density; usually chemical pure hydrogen consumption is 1.5～5.0% or higher (to stock oil weight), and the second reactive moieties average reaction temperature is general high more than 20 ℃, common higher more than 50 ℃, high more than 80 ℃ especially than the first reactive moieties average reaction temperature.The second reactive moieties operational condition is generally: temperature is that 300～480 ℃, pressure are that 6.0～25.0MPa, catalyst for refining volume space velocity are 0.1～2.0hr
-1, hydrogen/stock oil volume ratio is 500: 1～3000: 1.The second reactive moieties operational condition is preferably: temperature is that 320～440 ℃, pressure are that 10.0～20.0MPa, catalyst for refining volume space velocity are 0.2～0.5hr
-1, hydrogen/stock oil volume ratio is 1000: 1～2500: 1.On the full scale plant, second reactive moieties need be provided with many reactors, and the reactor outlet temperature is usually between 380～480 ℃.
As required, any additional sulphur can be added first reactive moieties,, guarantee that the necessary hydrogen sulfide sectional pressure of catalyzer is not less than minimum must value: such as 500PPm or 1000PPm to guarantee necessary minimum concentration of hydrogen sulfide.Described additional sulphur can be sulfide hydrogen maybe can be converted into sulfuration oxygen hydroconversion process is not had the material of undesirable action, such as hydrogen sulfide containing gas or oil product, or with dithiocarbonic anhydride that is converted into hydrogen sulfide after high-temperature hydrogen contacts or Methyl disulfide etc.
According to the present invention, the end reaction effluent enters cold high pressure separator after cooling through the high pressure heat transfer process, and the end reaction effluent enters before the cold high pressure separator, injects washing water to reaction effluent usually.Because coal tar nitrogen content height contains a large amount of ammonia in the reaction effluent, the washing water injection rate is big, causes end reaction effluent the injecting process temperature drop up to 40～60 ℃.Again because coal tar oxygen level height, contain a large amount of water generation reactions in the end reaction effluent, for preventing hydrochloric acid corrosion and ammonia chloride crystallization blocking pipe, washing water decanting point temperature is generally 190～240 ℃ (than 145～170 ℃ high of conventional crude cut fraction hydrogenation device washing water decanting point temperature many).
Described cold anticyclone separate part comprises cooling, the separating step of end reaction effluent after the water filling.At this, the end reaction effluent reduces temperature (using air-cooler and or watercooler usually) earlier usually to about 30～70 ℃, best 30～60 ℃ after the described water filling, in this temperature-fall period, water vapor is condensed into liquid phase gradually in the water filling afterreaction effluent, hydrogen sulfide in ammonia in the absorption reaction product and the further absorption reaction product forms high score water liquid.End reaction effluent cooling and in cold high pressure separator, being separated into after the final described water filling: a cold high score gas gas of mainly forming, a main cold high score fluid body and a main cold high score water liquid that form by water and that be dissolved with hydrogen sulfide, ammonia of forming by conventional liq hydrocarbon and dissolved hydrogen by hydrogen.Described cold high score water liquid, wherein the content of ammonia is generally 1～15% (w), is preferably 3～8% (w).
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 end reaction effluent, the liquid phase water yield must be greater than zero, be preferably the washing water total amount 30% or more, vaporize entirely to prevent water; On the other hand, the direct purpose of washing water is the ammonia in cold anticyclone separate part absorption reaction product, the ammonia concentration that prevents cold anticyclone separation gas is too high, gather at reactive system, reduce catalyst activity, usually the ammonia concentration of cold anticyclone separation gas is low more good more, generally is not more than 200PPm, preferably is not more than 50PPm; On the one hand, the direct purpose of another of washing water is the hydrogen sulfide in the absorption reaction product again, prevents that the 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.
Described cold anticyclone separate part, its separator operation pressure falls for reactive moieties pressure deducts true pressure, and the difference of cold anticyclone separate part working pressure and reactive moieties pressure should not be crossed lowly or too high, is generally 0.5～1.2MPa, is preferably 0.8MPa.
Described cold high score gas 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% described cold high score gas gas and return reactive moieties and form circulating hydrogen, so that necessary amounts of hydrogen of reactive moieties and hydrogen concentration to be provided; In order to improve plant investment efficient, must guarantee that the first 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 described cold high score gas gas of a part (hereinafter to be referred as cold high score gas discharging gas) to get rid of methane, the ethane that reaction produces.Discharge gas for cold high score gas, 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.
According to the present invention, reaction effluent is separated into recycle hydrogen and high-pressure separator hydrocarbon liquid through high pressure separation process (comprising the high pressure heat transfer process).Described high-pressure separator hydrocarbon liquid at first enters in the light pressure separator, is that 0.5～4.0MPa, temperature are under 35～60 ℃ of conditions at pressure usually, is separated into mainly by H
2And C
1, C
2Low minute gas gas that hydrocarbon is formed and mainly by C
3And low minute petroleum hydrocarbon liquid of above hydrocarbon composition.Then, the low oil that divides enters stabilizer tower (debutanizing tower or depentanizer or dehexanizing column or de-hydrogen sulfide column etc.), is under the operational condition of 0.8～2.3MPa at pressure, is separated into and is rich in C
3, C
4The stable overhead gas of hydrocarbon, mainly by C
3, C
4The stable cat head liquid hydrocarbon that hydrocarbon is formed and mainly by C
5And oil at the bottom of the stabilizer tower of above hydrocarbon composition.Oil further partly is separated into close-cut fraction product such as petroleum naphtha, diesel oil, wax oil etc. in fractionation at the bottom of the stabilizer tower.Separation column of the present invention can be the separation column that stabilizer tower or fractionation are partly used, and separation column of the present invention must use reboiler furnace or reboiler, and fractionation Tata low temperature of the present invention is generally 150～380 ℃, is preferably 250～360 ℃.
The coal tar hydrogenating conversion process, because the hydrogen consumption is high, so the exothermic heat of reaction amount is big, there is excessive heat energy in the intermediate reaction effluent; Because of easily reactive component is many in the raw material, reacting initial temperature is very low again, and the fuel oil preheating temperature is low, and there is excessive heat energy in the end reaction effluent.
Describe method of recovering heat in hydrocarbon hydrogenating conversion process of the present invention in detail below in conjunction with accompanying drawing.As shown in drawings, feed coal tar enters in the first reactive moieties reactor 3 through pipeline 1, hydrogen enters in the first reactive moieties reactor 3 through pipeline 2, the first reactive moieties reaction effluent enters in the second reactive moieties lead reactor 5 through managing 4, the second reactive moieties intermediate reaction effluent enters interchanger 7 and is cooled to the second reactive moieties low temperature intermediate reaction effluent and enters in the rearmounted reactor 9 of second reactive moieties through pipeline 8 through managing 6, the end reaction effluent enters that interchanger 11 cools and enters in the high-pressure separator 13 through pipeline 12 through managing 10, high score gas leaves high-pressure separator 13 tops and returns reactive moieties use after circulating hydrogen compressor boosts through managing 14, and high score oil leaves high-pressure separator 13 bottoms and removes light pressure separator through managing 15.
Low temperature heat-obtaining oil enters interchanger 7 and heats up with the heat exchange of intermediate reaction effluent, high temperature heat-obtaining oil enters separation column 23 bottoms through pipeline 22, after liquid phase stream mixes in the separation column, through pipeline 24, through pump 25, through pipeline 26, split into low temperature heat-obtaining oil and return interchanger 7 through pipeline 21 and recycle, the separation column bottoms is discharged through pipeline 30.Represented reboiler furnace flow process at the bottom of the fractionation Tata among the figure simultaneously, the liquid that heavily boils enters process furnace 28 heating through pipeline 27, and the thermogravimetric liquid that boils enters the separation column bottom through pipeline 29.
Represented simultaneously among the figure that low temperature heat-obtaining oil enters interchanger 11 and end reaction effluent heat exchange intensification, high temperature heat-obtaining oil enter separation column 23 bottoms through pipeline 222 situation through pipeline 211.
According to the present invention, described reaction effluent can be the intermediate reaction effluent, heat exchange this moment effect is to save cold hydrogen consumption, reduces the recycle hydrogen system scale, reduces the investment of recycle hydrogen system, and saving simultaneously divides the furnace fuel consumption, reduces and divide furnace scale and investment.
According to the present invention, described reaction effluent can be the end reaction effluent, and heat exchange this moment effect is to reclaim end reaction effluent heat energy, saves simultaneously and divides furnace fuel consumption, reduction to divide furnace scale and investment.
According to the present invention, described high temperature heat-obtaining oil can enter the branch furnace and further heat before returning the separation column bottom, and the total amount to reduce heat-obtaining oil and to divide furnace heavily to boil the liquid internal circulating load reduces the recycle pump energy consumption, reduces recycle system investment.
According to the present invention, in described heat-obtaining oil-circulation process, can use the logistics of interchanger heating process, steam takes place, hot water etc. takes place, also can use air cooler to reduce the heat-obtaining oil temperature and be used to discharge the heat of heat-obtaining oil in the surplus of reactive moieties absorption, be beneficial to and reduce follow-up high pressure heat exchanger material rate, reduce investment outlay.
According to the present invention, its operational condition is: the reaction effluent temperature is 300～480 ℃ and is preferably 380～440 ℃ that low temperature heat-obtaining oil temperature is 150～380 ℃ and is preferably 280～320 ℃; The temperature reduction is preferably 30～70 ℃ for 10～100 ℃ after the reaction effluent heat exchange.Temperature after the heat exchange of heat-obtaining oil can be by regulating the oil circulation amount control of heat-obtaining, the temperature after the heat exchange of heat-obtaining oil is general raise 30～150 ℃, should raise 50～90 ℃.
According to the present invention, reaction effluent is coal tar hydrogenating conversion reaction effluent or hydrogenation of shale oil conversion reaction effluent.
According to the present invention, use heat-obtaining oil, can pass through to regulate the oil circulation amount flexible of heat-obtaining heat-obtaining amount, thereby on exchange capability of heat, have bigger turndown ratio.
Major advantage of the present invention is:
1. to middle high temperature position reaction effluent heat energy, realize high potential temperature heat exchange, heat energy utilization rate height can reduce the high pressure heat exchanger scale, saves cold hydrogen consumption simultaneously, reduces cycle of higher pressure hydrogen system scale; Reclaim heat energy and be used to provide reboiling heat at the bottom of the fractionation Tata, but fuel saving consumption reduces reboiler or process furnace scale;
2. to final high potential temperature reaction effluent heat energy, realize high potential temperature heat exchange, reclaim heat energy and be used to provide reboiling heat at the bottom of the fractionation Tata, but fuel saving consumption reduces reboiler or process furnace scale;
3. on the other hand, according to the present invention, heat-obtaining oil heat exchanger (heat-obtaining oil heated up with this interchanger heat absorption when ordinary production was operated) can be used as hydrogenation unit and goes into operation with well heater (heat-obtaining is oily with this interchanger heat release when going into operation) use, at the hydrogenation unit temperature-rise period that goes into operation, operation conditions such as catalyst vulcanization process, use separation column reboiler furnace heating heat-obtaining oil, heat-obtaining oil circulation heating intermediate reaction effluent or the reactor feed of heating end reaction effluent indirect heating, because coal tar hydrogenating unit catalyzer air speed is very low, loaded catalyst is big, the present invention can significantly improve the device heat-up rate, the shortening cycle, reduce the thermal load and the investment of reaction raw materials (hydrogen and or stock oil) process furnace, so the present invention is unusual.
Embodiment
Coal tar hydrogenating unit, amount of finish 62.5t/h, coal tar character sees Table 1, and the reactive moieties operational condition sees Table 2, and embodiment of the present invention sees Table 3.
From table 3 column data as can be seen:
1. oil is cold heat-obtaining oil at the bottom of using separation column, reclaims heat energy 10.9MMkcal/h; Can save 4890 tons/year of separation column reboiler furnace standard fuels, be worth 1,900 ten thousand yuan/year;
2. save cold hydrogen 29100 standard cubes/time, reduce hydrogen gas circulating system and invest about 6,500,000 yuan;
3. reduce reaction feed process furnace thermal load 4.20MMkcal/h, reduce about 3,000,000 yuan of investment.
Although present embodiment is to be example with the coal tar hydrogenating unit, the characteristics of the present invention that it shows are suitable for the hydroconversion process that other high hydrogen consumes hydrocarbon hydrogenating conversion process such as shale oil equally.
The character of table 1 dehydrated coal tar
| Analysis project | Coal tar | |
| Density (20 ℃), g/ml | 1.06 | |
| Pour point, | 29 | |
| Total nitrogen, % (m/m) | 0.86 | |
| Sulphur content, % (m/m) | 0.16 | |
| The differential technique oxygen level, % (m/m) | 7.6 | |
| Charcoal, % (m/m) | 82.9 | |
| Hydrogen, % (m/m) | 6.51 | |
| Viscosity (100 ℃), mm 2/S | 7.1 | |
| Carbon residue, % | 5.9 | |
| Foreign metal content ug/g | Ca+Mg | 31 |
| Fe | 49 | |
| V | ＜0.1 | |
| Ni | ＜0.1 | |
| Na | 5 | |
| Boiling range ℃ | Initial boiling point | 131 |
| 5％ | ||
| 10％ | 220 | |
| 30％ | ||
| 50％ | 362 | |
| 70％ | 415 | |
| 90％ | 492 | |
| 95％ | 521 | |
| Do | ||
Table 2 operational condition summary sheet
| Operational condition | Numerical value | Remarks |
| Reactor 3 | ||
| Reactor inlet hydrogen dividing potential drop MPa | 15.3～17.0 | |
| Inlet amount (oil) t/h | 62.5 | |
| The reactor inlet hydrogen-oil ratio, m 3n/m 3 | 1300∶1～1800∶1 | |
| Catalyzer air speed h -1 | 0.50～1.00 | |
| Bed | 1 | |
| Reactor bed inlet temperature of reaction ℃ | 240～280 | |
| Reactor bed outlet temperature of reaction ℃ | 290～330 | |
| Reactor 5 | ||
| Catalyzer air speed h -1 | 0.40～0.8 | |
| Bed | 3～4 | |
| Reactor bed inlet temperature of reaction ℃ | 325～365 | |
| Reactor bed outlet temperature of reaction ℃ | 385～425 | |
| Reactor 9 | ||
| Catalyzer air speed h -1 | 0.40～0.8 | |
| Bed | 3～4 | |
| Reactor bed inlet temperature of reaction ℃ | 385～395 | |
| Reactor bed outlet temperature of reaction ℃ | 415～425 | |
| Overall chemical hydrogen consumption, m% | 3.5～5.5 | |
| High-pressure separator 13 | ||
| Working pressure MPa | 15.0～16.7 | |
| Service temperature ℃ | 40～60 | |
| Light pressure separator | ||
| Working pressure MPa | 1.5～2.7 | |
| Service temperature ℃ | 40～60 | |
| First separation column (stabilizer tower) | ||
| Working pressure MPa at the bottom of the tower | 1.56 | |
| Service temperature ℃ at the bottom of the tower | 355 | |
| After-fractionating tower (oil separation column at the bottom of the stabilizer tower) | ||
| Working pressure MPa at the bottom of the tower | -0.025 | |
| Service temperature ℃ at the bottom of the tower | 321 | |
Table 3 embodiment of the present invention
| Operational condition | Numerical value | Remarks |
| Cold heat-obtaining oil (oil at the bottom of the after-fractionating Tata) temperature ℃ | 312 | Heat-obtaining oil is other process-stream of heating earlier |
| Hot heat-obtaining oil temperature ℃ | 355 | |
| Interchanger 7 thermal loads, MMkcal/h | ～3.24 | Cold hydrogen amount save 2.9 ten thousand standard cubes/time |
| Pine for a reaction effluent temperature ℃ | 400 | |
| Cold intermediate reaction effluent temperature ℃ | 365 | |
| Interchanger 11 thermal loads, MMkcal/h | ～7.66 | |
| Hot end reaction effluent temperature ℃ | 415 | |
| Cold end reaction effluent temperature ℃ | 345 | |
| Heat-obtaining recovery of oil calorie distribution | ||
| The after-fractionating tower weight is boiling hot, MMkcal/h | 3.1 | |
| Other separation column reboiling heat, MMkcal/h | 2.4 | |
| The low oil that divides enters the preheating before of first separation column, MMkcal/h | 5.4 | |
Claims (8)
1, a kind of method of recovering heat in hydrocarbon hydrogenating conversion process is characterized in that comprising following steps:
1. the heat exchange of reaction effluent and low temperature heat-obtaining oil forms low-temp reaction effluent and high temperature heat-obtaining oil;
2. high temperature heat-obtaining oil enters separation column bottom, after liquid phase stream mixes in the separation column, splits into low temperature heat-obtaining oil again and returns step and 1. recycle.
2, method according to claim 1 is characterized in that: reaction effluent is the intermediate reaction effluent.
3, method according to claim 1 is characterized in that: reaction effluent is the end reaction effluent.
4, method according to claim 1 is characterized in that: high temperature heat-obtaining oil enters the separation column bottom after heating through the separation column reboiler furnace.
5, according to claim 1 or 2 or 3 or 4 described methods, it is characterized in that: the reaction effluent temperature is 300～480 ℃, and low temperature heat-obtaining oil temperature is 150～380 ℃; Temperature reduces by 10～100 ℃ after the reaction effluent heat exchange; Temperature raises 30～150 ℃ after the heat exchange of heat-obtaining oil.
6, method according to claim 5 is characterized in that: the reaction effluent temperature is 380～440 ℃, and low temperature heat-obtaining oil temperature is 280～320 ℃; Temperature reduces by 30～70 ℃ after the reaction effluent heat exchange; Temperature raises 50～90 ℃ after the heat exchange of heat-obtaining oil.
7, according to claim 1 or 2 or 3 or 4 described methods, it is characterized in that: reaction effluent is a coal tar hydrogenating conversion reaction effluent.
8, according to claim 1 or 2 or 3 or 4 described methods, it is characterized in that: reaction effluent is a hydrogenation of shale oil conversion reaction effluent.
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| CN101993718A (en) * | 2009-08-14 | 2011-03-30 | 山东三维石化工程股份有限公司 | Process for recovering heat energy of reaction product of hydrogenation device |
| CN101250434B (en) * | 2008-03-31 | 2011-12-14 | 中国石油化工集团公司 | Hydrocarbons hydrogenation conversion method |
| CN101289631B (en) * | 2008-03-12 | 2012-08-29 | 上海优华系统集成技术有限公司 | Optimizing hydrogenation and heat-exchange system |
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| CN112745954A (en) * | 2015-08-24 | 2021-05-04 | 沙特阿拉伯石油公司 | Recovery and reuse of waste energy in industrial plants |
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