CN102021045B - Method for separating mixed gas containing tar - Google Patents
Method for separating mixed gas containing tar Download PDFInfo
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Abstract
The invention discloses a method for purifying a mixed gas containing tar, wherein the mixed gas containing tar comprises carbon monoxide, hydrogen, methane, carbon dioxide, tar and water. The method comprises the following steps of: 1. contacting the mixed gas containing tar with an organic solvent for 10s-120s to obtain a fist gaseous product and a fist liquid product, wherein the temperature of the organic solvent is 70-200 DEG C; 2. separating out the first liquid product; and 3. cooling the fist mixed gas to obtain purified gas and a second liquid product, and separating out the second liquid product. By using the method for purifying a mixed gas containing tar, coal tar oil and light oil with water content of lower than 1wt% can be obtained directly, and oil content of separated water is lower than 200mg/L.
Description
Technical field
The invention relates to a kind of separation method that contains the gas mixture of tar.
Background technology
Coal preparing natural gas technological line, at present take the international coal preparing natural gas of big plain in u.s.a demonstration unit (20 years of operation) and Datang project as representative, mainly adopt the Shandong strange/crushed coal pressure gasifying, the oil resistant of anti-sulphur conversion, low-temperature rectisol purify and methanation.Typical technical process is first the coal of extraction in the colliery to be carried out the coal choosing, is divided into broken coal, coal dust and coal gangue, and broken coal is used for pressurized gasification, and coal dust is used for destructive distillation, and coal gangue coordinates with coal dust and/or broken coal for boiler generation steam and generating.The principal reaction of crushed coal pressure gasifying is coal and the reaction of steeping in water for reconstitution unboiled water coal gas, obtains raw gas, and the main component of raw gas is synthetic gas (comprising carbon monoxide, hydrogen and methane), also has the undecomposed water of part, and a small amount of coal tar component.The fine coal destructive distillation is that fine coal is heated under isolated air, makes it to be decomposed into the process of gas such as coal gas, liquid such as tar and solid (as coke).General destructive distillation is carried out in upright furnace, and this upright furnace generally comprises dryer section, retort section and cooling section from top to bottom.at first feed coal enters the dryer section on stove top, the hot gas flow that utilizes retort section to produce carries out preheating to feed coal, then be displaced downwardly to retort section and carry out destructive distillation, the solid product high temperature semicoke that destructive distillation obtains is immersed in the water and extinguishes and produce a large amount of water vapour, water vapour rises to be combined with the high temperature semicoke and produces a large amount of water-gas, water-gas rises to the airway of furnace roof and derives, the gas of deriving from airway is commonly referred to as raw gas, the coal gas that raw gas is mainly produced by destructive distillation in stove, hot waste gas after heating, from the water-gas of cooling section rising and the steam of dried feed coal generation, specifically can be referring to the disclosed low-temperature coal carbonization manufacturing technique of CN1966612A.
From foregoing description as can be known, crushed coal pressure gasifying and the dry distillation of coal all produce carbon monoxide and hydrogen is the raw gas of main component, and the further methanation of carbon monoxide and hydrogen obtains methane gas (being SNG).In the gas product of coal process for producing natural gained, the content of methane can be up to 96%, calorific value 35564kJ/m
3Above.
Yet, can be found out by the flow process of foregoing description, the pressurized gasification of broken coal all must separate by product raw gas or the raw gas that chilling separates obtaining with the dry distillation of coal.In the chilling separating technology, the general water that adopts is as refrigerant, for example, CN1318550C discloses a kind of process for pressurized gasification of dry coal fines, wherein water is directly contacted with raw gas or raw gas, make all boiling points comprise that higher than the material of normal temperature dust all enters subsider together, collect gas-phase product, light oil flows out from the surface, and tar-bitumen is told from the lower end, the centre is the oily(waste)water that contains phenol and ammonia, and oily(waste)water is mainly by the part oil phase and water is miscible forms.Come from water contained in gas mixture because water comprises, also comprise the water that comes from as the chilling agent, therefore, the amount of oily(waste)water is larger.The aftertreatment of oily(waste)water generally processes to remove wherein coal tar by Multistage settling.Yet the water after Multistage settling is processed also contains the oil that nearly 1000mg/ rises, and also needs further to carry out follow-up deamination dephenolizing process after removing coal tar again, thereby reaches process water reuse or emission standard.This shows, the processing of oily(waste)water causes the water treatment expense to increase, and therefore, oily(waste)water is treated as the main weak point of selecting crushed coal pressure gasifying in coal preparing natural gas project.
In addition, US4324643 discloses a kind of method that is prepared stable hydro carbons by the solid particulate carbonaceous material, the method comprises 1) be enough to produce the described solid particulate carbonaceous material of thermo-cracking under the temperature and pressure condition of gas-solid mixture, described gas-solid mixture contains granular solids and hot pyrolysis gas product, and described gas products contains the above macromole hydrocarbon of 4 carbon atoms and the instant volatile hydrocarbon free radical that generates in reaction; 2) gas solid separation obtains substantially not containing the gaseous mixture of solid; 3) the described gaseous mixture that does not substantially contain solid is mixed with the quench liquid that contains end-capping reagent, the condition of chilling makes the volatile hydrocarbon free radical of instant generation in reaction almost can all react and termination reaction with end-capping reagent simultaneously, and make the condensation simultaneously of most of at least described macromole hydrocarbon, thereby obtain gas and condensation and stable hydrocarbon.And the temperature that further discloses condensation is particularly preferably lower than 200 °F (namely 95 ℃), and condensed fluid is mainly hydrocarbon.
Although adopt hydrocarbon can reduce the amount of water in system to be separated as the main component of condensing agent, yet aforesaid method can not really solve the oily(waste)water problem.
Summary of the invention
The objective of the invention is in order to overcome the defects of prior art, a kind of separation method of the gas mixture that contains tar newly is provided.
in order to solve the oily(waste)water problem of above-mentioned prior art, the present inventor has carried out a large amount of research, found that, be that the organic solvent (namely oily) of 70-200 ℃ contacts with the gas mixture that contains tar by adopting temperature, and the time that the control raw gas contacts with organic solvent is 10 seconds to 120 seconds, successfully realized being separated between organism that water in the raw gas and coal tar wet goods produce oily(waste)water, make water and coal tar enter respectively gas phase and liquid phase, and by making further cooling and oily water separation of gas phase, system's waste water oleaginousness is down to below 200mg/L, even be low to moderate below 50mg/L.
The invention provides a kind of purifying method that contains the gas mixture of tar, this gas mixture that contains tar contains carbon monoxide, hydrogen, methane, carbonic acid gas, tar and water, and the method comprises the following steps:
(1) the described gas mixture that contains tar is contacted with organic solvent, the condition of contact comprises that the temperature of organic solvent is 70-200 ℃, and the time is 1 second to 120 seconds, obtains the first gaseous product and the first liquid product;
(2) isolate the first liquid product;
(3) described the first gaseous product is cooling, obtain purified gas and the second liquid product, isolate the second liquid product.
The separation method of the gas mixture that contains tar provided by the invention is by adopting oil directly to contact with the gas mixture that contains tar, and the temperature and time of control contact, make the tar that causes forming oily(waste)water form respectively mutually different with water, be separated with realization, directly obtain water content less than coal tar and the light oil of 1 % by weight, in isolated water, oil-contg less than 200 mg/litre, only contains a small amount of ammonia and phenol.Thereby efficiently solve the oily(waste)water problem.This shows, adopt method provided by the invention can reduce the cost of wastewater treatment.Method provided by the invention can be used for the various separation that can produce the mixed gas that contains tar of oily(waste)water problem.
experimental results show that, the temperature of organic solvent is during lower than 70 ℃, although in theory by foreshortening to the duration of contact that makes organic solvent and raw gas when being less than 10 seconds, also can realize and can realize fast the described cooling that contains the gas mixture of tar, make the described temperature that contains the gas mixture of tar be reduced to lower than tar condensing temperature (being liquefaction temperature) and higher than the dew-point temperature of water, but, because the temperature of organic solvent is too low, heat exchange between gas mixture and organic solvent is too rapid, cause between gas mixture and organic solvent contact abundant not, thereby dissolving or the moisture that is included in the tar of gas mixture have little time to overflow from tar, and be separated with water in oil liquid phase emulsion droplet form and the gas phase composition of having overflowed, thereby the liquid phase that obtains is a large amount of water in oil liquid phase emulsion droplet, can not really realize separating fully of tar and water, also just can not really solve the oily(waste)water problem.
on the contrary, the temperature of organic solvent is during higher than 200 ℃, although the duration of contact by extending organic solvent and gas mixture is during more than 120 seconds, also can realize the described cooling that contains the gas mixture of tar, make the described temperature that contains the gas mixture of tar be reduced to lower than tar condensing temperature (being liquefaction temperature) and higher than the dew-point temperature of water, but, excess Temperature due to organic solvent, described gas mixture and the heat exchange between organic solvent that contains tar is too slow, cause the described gas mixture that contains tar to be in for a long time the condition of high temperature, and owing to containing a large amount of unsaturated hydrocarbons in tar, these unsaturated hydrocarbons are easy to occur further polymerization under the above-mentioned condition of high temperature, cause the viscosity of tar further to increase, formation is more prone to Jiao of thickness attitude, the content of oil further reduces.In this case, the water that does not have enough time to overflow in tar just is covered by in Jiao of this thickness attitude, and more difficult realization separates.
Description of drawings
Fig. 1 is the process flow sheet of the separation method of the gas mixture that contains tar provided by the invention.
Embodiment
In the present invention, the described gas mixture that contains tar can be that the various boiling points that contain simultaneously are higher than the gas mixture of tar, water and the carbon monoxide of water, hydrogen, methane, carbonic acid gas, for example, can be the gas mixture that crushed coal pressure gasifying produces, can be also the gas mixture that coal medium temperature carbonization, low-temperature pyrolysis produce.
The described starting temperature that contains the gas mixture of tar is not particularly limited, as long as water wherein exists with vapor form, is generally 80-750 ℃, is preferably 100-650 ℃; Pressure can high pressure, normal pressure, also can be pressure-fired, for example can be the 0.08-6 MPa, is preferably the 0.1-4 MPa.For different sources, the condition of gas mixture that contains tar is different.For example, for the gas mixture that crushed coal pressure gasifying produces, temperature is generally 150-750 ℃, is preferably 250-650 ℃; Pressure is generally the 1-10 MPa, is preferably the 2-6 MPa, more preferably the 2-4 MPa.For the gas mixture that the dry distillation of coal produces, temperature is generally 80-200 ℃, is preferably 90-180 ℃, and pressure is generally the 0.08-0.3 MPa, is preferably the 0.1-0.13 MPa.
In the present invention, tar can be the black organism that various boiling points are high and viscosity is large, and its boiling point is generally up to more than 160 ℃.Carbon monoxide in gas mixture, hydrogen, methane, carbonic acid gas are gaseous component at normal temperatures.
Be the component and tar and water of gaseous component under above-mentioned normal temperature, also contain boiling point in common described gas mixture and ought for example be no more than the organic constituent of 180 ℃ lower than water or with water, originate different, concrete components because of the gas mixture that contains tar can be different.For example, for crushed coal pressure gasifying and the dry distillation of coal, gained contains light component in the gas mixture of tar and usually also comprises under normal temperature for liquid liquid ingredient such as phenol, biphenol, formic acid, gasoline, boiling point lower than one or more in the petroleum naphtha of 180 ℃.Therefore these components all are present in described the first gaseous product with gas form under the condition of described contact due to more volatile or very easily water-soluble.In order to take full advantage of the various useful components oil particularly in the above-mentioned gas mixture that contains tar, under preferable case, method provided by the invention also comprises carries out oily water separation with the second liquid product.
According to the separation method that contains the gas mixture of tar provided by the invention, although be 70-200 ℃ as long as control the temperature of the organic solvent that contacts with described raw gas, time is 10 seconds to 120 seconds, can obtain the first gas-phase product and the first liquid product, reaches purpose of the present invention.But under preferable case, in order further to improve separating of coal tar and water in raw gas, the condition that described raw gas contacts with organic solvent comprises that the temperature of organic solvent is 80-180 ℃, and the time is 10-100 second, further preferred temperature is 80-150 ℃, and the time is 20-50 second.
And experimental results show that, when the described temperature that contains the gas mixture of tar is 150-750 ℃, when pressure was the 2-6 MPa, the temperature of controlling described organic solvent was that 70-200 ℃, duration of contact are 10-120 second, the consumption of described organic solvent be the described gas mixture weight that contains tar 1-15 doubly; The preferred described temperature that contains the gas mixture of tar is 250-650 ℃, and pressure is the 2-4 MPa, and the temperature of controlling described organic solvent is that 80-150 ℃, duration of contact are 10-50 second, the consumption of described organic solvent be the described gas mixture weight that contains tar 1-5 doubly.in above-mentioned scope particularly in the optimum condition scope, can prevent because the temperature of organic solvent is too low, the gas mixture and the heat exchange between organic solvent that contain tar are too rapid, contacting between the gas mixture that contains tar that causes and organic solvent may be abundant not, thereby dissolving or the moisture that is included in the tar of the gas mixture that contains tar may have little time to overflow from tar, and be separated with water in oil liquid phase emulsion droplet form and the gas phase composition of having overflowed, thereby the liquid phase that obtains is a large amount of water in oil liquid phase emulsion droplet, can not really realize separating fully of tar and water, also just may not really solve the oily(waste)water problem, can also prevent the excess Temperature due to organic solvent, the gas mixture and the heat exchange between organic solvent that contain tar are too slow, the gas mixture that contains tar that causes may be in the condition of high temperature for a long time, and owing to containing a large amount of unsaturated hydrocarbons in tar, these unsaturated hydrocarbons are easy to occur further polymerization under the above-mentioned condition of high temperature, cause the viscosity of tar further to increase, form Jiao who is more prone to the thickness attitude, the content of oil further reduces.In this case, the water that does not have enough time to overflow in tar just is covered by in Jiao of this thickness attitude, and more difficult realization separates.
The above-mentioned gas mixture that contains tar is for example raw gas for the crushed coal pressure gasifying product, this contains in the gas mixture of tar, the content of described water is generally the described 10-60 % by weight that contains the raw gas of tar, 25-50 % by weight more preferably, the 0.1-20 % by weight of the raw gas total amount outside the content of tar is generally and dewaters, be preferably the 2-10 % by weight, more preferably the 3-6 % by weight.That is to say, suppose that the content of water in the described gas mixture that contains tar is 30 % by weight, the content of tar is the described 0.7-14 % by weight that contains tar gas mixture total amount for the 0.1-20 % by weight in remaining 70 % by weight, preferred 0.35-10.5 % by weight.
Owing to making the water in described raw gas keep gaseous state temperature required closely related with pressure, make the water in described raw gas keep gaseous state temperature required also different under different pressures.In order to reduce as far as possible the consumption as the organic solvent of refrigerant, the present invention preferably uses the large as far as possible organic solvent of gasification latent heat, the gasification latent heat of concrete preferred described organic solvent is greater than 50 kilojoule per kilogram, 50-2000 kilojoule per kilogram for example, the gasification latent heat of further preferred organic solvent is the 150-1000 kilojoule per kilogram.When the gasification latent heat of described organic solvent is the 50-2000 kilojoule per kilogram, the condition of described contact comprise the consumption of described organic solvent be described raw gas weight 1-15 doubly, the time of contact is can realize making the temperature of described raw gas to be reduced to 200-300 ℃ in 10 seconds to 120 seconds; When the gasification latent heat of described organic solvent is the 150-1000 kilojoule per kilogram, the condition of described contact comprises that the consumption of described organic solvent is 2-10 times of described raw gas weight, and the time of contact is that 10-45 can realize making the temperature of described raw gas to be reduced to 200-300 ℃ second.
In the present invention, unless stated otherwise, described gasification latent heat refers to 1 gasification latent heat under normal atmosphere.Boiling point refers to the boiling point under standard state.
and the temperature that ought describedly contain the gas mixture of tar is 80-200 ℃, pressure is the 0.08-0.3 MPa, the temperature of controlling organic solvent is 80-120 ℃, be 10-120 second duration of contact, the consumption of described organic solvent be the described gas mixture that contains tar weight 0.5-5 doubly, the preferred described temperature that contains the gas mixture of tar is 90-180 ℃, pressure is the 0.1-0.13 MPa, the temperature of controlling organic solvent is 80-120 ℃, be 5-50 second duration of contact, the consumption of described organic solvent also can effectively prevent above-mentioned organic solvent temperature too high or duration of contact of the oversize oily(waste)water problem that causes when being 1-3 times of the described gas mixture weight that contains tar.
The described gas mixture that contains tar can be the product of various destructive distillation products such as the dry distillation of coal, the biomass carbonization such as stalk etc., shale oil destructive distillation, oil-sand destructive distillation.In above-mentioned destructive distillation obtains the described gas mixture that contains tar, described outside the content of tar is generally and dewaters contains the 1-25 % by weight of total amount of the gas mixture of tar, and the content of water is generally the 1-30 % by weight.
According to the present invention, when the described mixture temperature that contains tar is higher, when particularly wherein tar was gas phase, described organic solvent was refrigerant or chilling agent with respect to the described gas mixture that contains tar; And the mixture temperature that ought describedly contain tar is lower, and during especially lower than the boiling temperature of water, described organic solvent is thermal source with respect to the described gas mixture that contains tar.
On the other hand, in above-mentioned two situations, described organic solvent also plays washing composition or extraction agent, by contacting between described organic solvent and the described gas mixture that contains tar, described organic solvent with the organic composition in the described gas mixture that contains tar particularly tar wash or extract.
In the present invention, described organic solvent can be single solvent, can be also the mixed solvent of multiple organic solvent.Industrial preferred use boiling range as one or more in coal tar, hydrocracking tail oil, diesel oil and the wax oil of 180-500 ℃ as described organic solvent.
Further under preferable case, the tar of at least part of described organic solvent for obtaining by separating the described gas mixture that contains tar, also be about to the liquid product of described step (1) gained partly or entirely as described organic solvent, can reduce the amount of outsourcing organic solvent so on the one hand, save production cost, the liquid product that has also solved on the other hand step (1) gained is the emission problem of tar.
According to method provided by the invention, the contacting of the described gas mixture that contains tar and described organic solvent is that the direct method of contact, the mode of described direct contact can be that the described gas mixture that contains tar is with the organic solvent counter current contact or and stream contact or adverse current also flows the mode of carrying out simultaneously.
For organic solvent is fully contacted with the gas mixture that contains tar, effectively carry out heat exchange, washing (tar in the described gas mixture that contains tar being washed by organic solvent), the present invention preferably can make described organic solvent contact with the gas mixture that contains tar with vaporific form by accessory in liquid distributor or spraying gun or other tower containers.
According to method provided by the invention, the product that the gained tower top is overflowed is further cooling is in order to make oil phase and the gas delivery in water and light component, therefore cooling temperature so that water can be cooled to liquid state is as the criterion, preferably is cooled to 10-60 ℃, further preferred 20-50 ℃.Can realize simultaneously separating of gaseous fraction, lightweight oil phase and water like this, improve the yield of separation efficiency and lightweight oil phase.
Because the present invention only relates to improvement to the separation method of the gas mixture that contains tar, therefore, the described preparation method that contains the gas mixture of tar can be method well known in the art, for example, can adopt crushed coal pressure gasifying method well known in the art to obtain or adopt dry distillation of coal method well known in the art to obtain.Described broken coal can be to be not less than the various broken coal pieces of 5 millimeters, and for example size is the broken coal piece of 5-80 millimeter.Described pressurized gasification condition comprises that the bottom temp of plus-pressure furnace is 1000-1500 ℃, and outlet mixed gas temperature can be 150-750 ℃, and pressure can be the 2-6 MPa, and preferred temperature is 250-650 ℃, and pressure is the 2-4 MPa.Described pressurized gasification can carry out in various vapourizing furnaces known in the art, for example, can carry out in pressurized-gasification furnace, upright furnace, lurgi gasifier at crushed coal pressure gasifying.The method of the described dry distillation of coal can be low-temperature pyrolysis, also can medium temperature carbonization, and can also be high temperature carbonization.The destructive distillation condition comprises that the bottom temp of gas retort is 800-1100 ℃, and the top gas temperature out can be the 0.08-0.3 MPa for 500-750 ℃, pressure.The coal that is used for destructive distillation can be fine coal and/or broken coal, and described fine coal can be that all size is no more than the fine coal of 5 millimeters.Described destructive distillation can be carried out in various vapourizing furnaces known in the art, for example, can carry out in conventional upright furnace, lurgi gasifier or the fluidized bed dry distillation technique stove that uses in destructive distillation field.
According to one embodiment of the present invention, the separation method of the described gas mixture that contains tar as shown in Figure 1.gas mixture such as the raw gas that will contain tar directly contact with organic solvent in gas-liquid separator such as chilling separator, obtain the first gaseous product and the first liquid product, composition in the described gas mixture that contains tar outside tar removing as the component that is gaseous state under water and normal temperature substantially or all as described in the first gaseous product, whole or most tar are in described the first liquid product, with described the first gaseous product in interchanger such as condenser further heat exchange be cooling after, obtain the second gaseous product (being mainly the component that is gaseous state under normal temperature) and the second liquid product (being mainly water and lightweight oil), by further oily water separation, obtain water and lightweight oil.Water can be cycled to used in pressurized gasification or distillation process.
The present invention is described further for the following examples.
Embodiment 1
This embodiment is used for illustrating the separation method that contains the gas mixture of tar provided by the invention.
Adopt technique shown in Figure 1, water vapor and size are sent into weight ratio and carried out pressurized gasification in vapourizing furnace for the brown coal broken coal of 5-50 millimeter (relevant physical property sees table 1 for details) at 1: 1, the bottom temp of vapourizing furnace is 1200 ℃, head temperature is 500 ℃, base pressure is 3.5MPa, top pressure is 3MPa, obtain pressure and be 3MPa, temperature and be the gas mixture that the crushed coal pressure gasifying product of 500 ℃ namely contains tar and discharge (composition outside dewatering is as shown in table 2, and the content of water is 30 % by weight of crushed coal pressure gasifying product total amount) from top of gasification furnace.
then be 3 MPas with this pressure, temperature is that the crushed coal pressure gasifying product of 500 ℃ is take the flow of 1000 kg/hrs and temperature as 100 ℃, boiling range is 180-500 ℃, flow is that the coal tar of 2800 kg/hrs contacts in the chilling separator, contact after 25 seconds, be that the first liquid product (temperature is 280 ℃) is discharged at the bottom of tower with liquid product, in contact process, gas-phase product i.e. the first gaseous product (temperature is 200 ℃) is overflowed from tower top, gas-phase product is further sent in subsider by after interchanger indirect heat exchange to 50 ℃, collection is from subsider top escaping gas component (synthetic gas), with the standing natural layering of the liquid in subsider, isolate wherein water and organic phase.Result is that water is transparent, and oleaginousness is 50mg/L.At the bottom of tower, liquid product learns that by analysis water content is 0.2 % by weight.
Embodiment 2
This embodiment is used for illustrating the separation method that contains the gas mixture of tar provided by the invention.
Adopt technique shown in Figure 1, water vapor and size are sent into weight ratio and carried out pressurized gasification in vapourizing furnace for the brown coal broken coal of 5-50 millimeter (relevant physical property sees table 1 for details) at 1: 1, the bottom temp of vapourizing furnace is 1000 ℃, head temperature is 300 ℃, base pressure is 3MPa, top pressure is 2.5MPa, the crushed coal pressure gasifying product that obtains pressure and be 2.5 MPas, temperature and be 300 ℃ is discharged (composition outside dewatering is as shown in table 2, and the content of water is 50 % by weight of crushed coal pressure gasifying product total amount) from the top.
then be 2.5 MPas with this pressure, temperature is that the crushed coal pressure gasifying product of 300 ℃ is take the flow of 1500 kg/hrs and temperature as 150 ℃, boiling range is 280-480 ℃, flow is that the hydrocracking tail oil of 2200 kg/hrs contacts in the chilling separator, contact after 40 seconds, liquid product (temperature is 280 ℃) is discharged at the bottom of tower, gas-phase product (temperature is 210 ℃) is overflowed from tower top, gas-phase product is further sent in subsider by after interchanger indirect heat exchange to 40 ℃, collection is from subsider top escaping gas component (synthetic gas), with the standing natural layering of the liquid in subsider, isolate wherein water and organic phase, the discovery water is transparent, oleaginousness is 100mg/L.At the bottom of tower, liquid product learns that by analysis water content is 0.3 % by weight.
Embodiment 3
This embodiment is used for illustrating the separation method that contains the gas mixture of tar provided by the invention.
Adopt technique shown in Figure 1, water vapor and size are sent into weight ratio and carried out pressurized gasification in vapourizing furnace for the brown coal broken coal of 5-50 millimeter (relevant physical property sees table 1 for details) at 1: 1, the bottom temp of vapourizing furnace is 1300 ℃, head temperature is 650 ℃, base pressure is 4MPa, top pressure is 3.5MPa, the crushed coal pressure gasifying product that obtains pressure and be 3.5 MPas, temperature and be 650 ℃ is discharged (composition outside dewatering is as shown in table 2, and the content of water is 20 % by weight of crushed coal pressure gasifying product total amount) from the top.
then be 3.5 MPas with this pressure, temperature is that the crushed coal pressure gasifying product of 650 ℃ is take the flow of 800 kg/hrs and temperature as 80 ℃, boiling range is 180-500 ℃, flow is that the coal tar of 2500 kg/hrs contacts in the chilling separator, contact after 30 seconds, liquid product (temperature is 260 ℃) is discharged at the bottom of tower, gas-phase product (temperature is 190 ℃) is overflowed from tower top, gas-phase product is further sent in subsider by after interchanger indirect heat exchange to 40 ℃, collection is from subsider top escaping gas component (synthetic gas), with the standing natural layering of the liquid in subsider, isolate wherein water and organic phase, the discovery water is transparent, oleaginousness is 150mg/L.At the bottom of tower, liquid product is learnt water content 0.4 % by weight by analysis.
Comparative Examples 1
Method according to embodiment 1 is obtained synthetic gas, and different is, the temperature of coal tar is 50 ℃, and the time of contact is 10 seconds, obtains gaseous fraction (synthetic gas), water and oil phase.Result is that water is opaque, and oleaginousness is 500mg/L.At the bottom of tower, liquid product learns that by analysis water content is 2 % by weight.
Embodiment 4
This embodiment is used for illustrating the separation method that contains the gas mixture of tar provided by the invention.
Adopt technique shown in Figure 1, the long-flame coal lump coal (relevant physical property sees table 1 for details) that is 25-80mm with size carries out destructive distillation in upright furnace, the bottom temp of upright furnace is 900 ℃, temperature after the raw gas ammonia spray is 100 ℃, base pressure is 0.14MPa, and top pressure is 0.11MPa, obtains pressure and be 0.11MPa, temperature and be the gas mixture that the raw gas of 100 ℃ namely contains tar, composition outside raw gas dewaters is as shown in table 3, and water-content is 30 % by weight of raw gas total amount.
then with this raw gas take double centner/hour flow and temperature as 180 ℃, boiling range is 180-500 ℃, flow is the coal tar contact of 200 kg/hrs, contact after 100 seconds, liquid product i.e. the first liquid product is discharged at the bottom of tower, gas-phase product is that (temperature is 100 ℃ to the first gaseous product, pressure is 0.11 MPa) overflow from tower top, gas-phase product is further sent in subsider by after interchanger indirect heat exchange to 50 ℃, collection is purified gas from subsider top escaping gas component, with the standing natural layering of the liquid in subsider, isolate wherein water and organic phase.The discovery water is transparent, oleaginousness 60mg/L.At the bottom of tower liquid product by analysis, water content is 0.1 % by weight.
Embodiment 5
This embodiment is used for illustrating the separation method that contains the gas mixture of tar provided by the invention.
Adopt technique shown in Figure 1, the long-flame coal lump coal (relevant physical property sees table 1 for details) that is 25-80mm with size carries out destructive distillation in upright furnace, the bottom temp of upright furnace is 700 ℃, temperature after the raw gas ammonia spray is 160 ℃, base pressure is 0.12MPa, and top pressure is 0.106MPa, and obtaining pressure is that 0.108MPa, temperature are the raw gas of 160 ℃, composition outside raw gas dewaters is as shown in table 3, and water-content is 0.05 times of weight of the total amount of the described gas mixture that contains tar.
then with this raw gas take double centner/hour flow and temperature as 90 ℃, boiling range is 180-500 ℃, flow be double centner/hour coal tar contact, contact after 60 seconds, liquid product is discharged at the bottom of tower, (temperature is 160 ℃ to gas-phase product, pressure is 0.106 MPa) overflow from tower top, gas-phase product is further sent in subsider by after interchanger indirect heat exchange to 50 ℃, collection is synthetic gas from subsider top escaping gas component, with the standing natural layering of the liquid in subsider, isolate wherein water and organic phase, the discovery water is transparent, oleaginousness is 110mg/L.At the bottom of tower liquid product by analysis, water content is 0.5 % by weight.
Embodiment 6
This embodiment is used for illustrating the separation method that contains the gas mixture of tar provided by the invention.
Adopt technique shown in Figure 1, the long-flame coal lump coal (relevant physical property sees table 1 for details) that is 25-80mm with size carries out destructive distillation in upright furnace, the bottom temp of upright furnace is 850 ℃, temperature after the raw gas ammonia spray is 180 ℃, base pressure is 0.13MPa, and top pressure is 0.102MPa, and obtaining pressure is that 0.102MPa, temperature are the raw gas of 180 ℃, composition outside raw gas dewaters is as shown in table 3, and water-content is 0.1 times of weight of purified gas total amount.
then with this raw gas take double centner/hour flow and temperature as 100 ℃, boiling range is 180-500 ℃, flow be double centner/hour coal tar contact, contact after 20 seconds, liquid product is discharged at the bottom of tower, (temperature is 180 ℃ to gas-phase product, pressure is 0.102 MPa) overflow from tower top, gas-phase product is further sent in subsider by after interchanger indirect heat exchange to 50 ℃, collection is synthetic gas from subsider top escaping gas component, with the standing natural layering of the liquid in subsider, isolate wherein water and organic phase, the discovery water is transparent, oleaginousness is 120mg/L.At the bottom of tower liquid product by analysis, water content is 0.3 % by weight.
Comparative Examples 2
Method according to embodiment 4 is obtained raw gas, and different is, the temperature of coal tar is 300 ℃, and the time of contact is 300 seconds, obtains gaseous fraction (synthetic gas), water and oil phase.Result is that water is translucent, and oleaginousness is 1200mg/L.At the bottom of tower liquid product by analysis, water content is 3 % by weight.
Table 1
| Project | Brown coal | Long-flame coal (sub-bituminous coal) |
| Technical analysis (% by weight) War Wad Aad Vad Sad | 36.90 17.81 12.02 29.49 1.21 | 8.00 7.39 21.90 35.17 0.36 |
| Ultimate analysis (% by weight) Car Har Oar Nar Sar | 52.23 3.20 12.06 0.61 1.21 | 53.75 4.15 11.43 1.02 0.36 |
| Ash fusion point (℃) T1 T2 T3 | 1160 1200 1220 | 1420 greater than 1500 greater than 1500 |
Annotate:
War---represent coal-fired moisture as received coal; Wad---the coal-fired dry basic moisture of expression; Har---represent that coal-fired as received basis hydrogen divides; Aad---the coal-fired dry basic ash content of expression; Vad---the coal-fired dry basic volatile matter of expression; Sad---the coal-fired dry basic sulphur content of expression; Car---represent that coal-fired as received basis carbon divides; Oar---represent that coal-fired as received basis oxygen divides; Nar---represent that coal-fired as received basis nitrogen divides; Sar---represent coal-fired as received basis sulphur content; T1---softening temperature, ℃; T2---hemispherical temperature, ℃; T3---melt temperature, ℃.
Table 2
| Form (% by weight) | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 |
| H 2 | 3.59 | 3.61 | 3.58 | 3.59 |
| CO | 19.68 | 19.75 | 19.56 | 19.68 |
| CO 2 | 62.88 | 63.09 | 62.71 | 62.88 |
| CH 4 | 7.57 | 7.35 | 7.65 | 7.57 |
| N 2 | 0.34 | 0.34 | 0.34 | 0.34 |
| C 2 | 0.39 | 0.36 | 0.39 | 0.39 |
| C 3 | 0.39 | 0.35 | 0.39 | 0.39 |
| H 2S | 0.50 | 0.50 | 0.51 | 0.50 |
| NH 3 | 0.17 | 0.17 | 0.17 | 0.17 |
| HCN | 0.01 | 0.01 | 0.01 | 0.01 |
| C 6H 6O | 0.39 | 0.39 | 0.39 | 0.39 |
| C 6H 6O 2 | 0.26 | 0.26 | 0.26 | 0.26 |
| Petroleum naphtha (＜180 ℃) | 0.41 | 0.38 | 0.41 | 0.41 |
| Middle oil (180-360 ℃) | 1.60 | 1.57 | 1.70 | 1.60 |
| Heavy oil (＞360 ℃) | 1.82 | 1.87 | 1.93 | 1.82 |
| ∑ | 100.00 | 100.00 | 100.00 | 100.00 |
| The oil product total amount | 4.48 | 4.47 | 4.69 | 4.48 |
Table 3
| Form (% by weight) | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative Examples 2 |
| H 2 | 5.73 | 5.50 | 5.69 | 5.73 |
| CO | 30.89 | 30.85 | 30.83 | 30.89 |
| CO 2 | 14.00 | 13.84 | 13.97 | 14.00 |
| CH 4 | 23.50 | 23.93 | 23.67 | 23.50 |
| N 2 | 7.96 | 7.85 | 7.94 | 7.96 |
| C 2 | 1.52 | 1.55 | 1.51 | 1.52 |
| C 3 | 1.99 | 2.02 | 1.99 | 1.99 |
| H 2S | 0.92 | 0.91 | 0.92 | 0.92 |
| NH 3 | 0.26 | 0.24 | 0.24 | 0.26 |
| HCN | 0.02 | 0.02 | 0.02 | 0.02 |
| C 6H 6O | 0.13 | 0.13 | 0.13 | 0.13 |
| C 6H 6O 2 | 0.07 | 0.07 | 0.07 | 0.07 |
| Petroleum naphtha (＜180 ℃) | 1.97 | 1.99 | 1.98 | 1.97 |
| Middle oil (180-360 ℃) | 4.29 | 4.28 | 4.30 | 4.29 |
| Heavy oil (＞360 ℃) | 6.75 | 6.82 | 6.74 | 6.75 |
| ∑ | 100.00 | 100.00 | 100.00 | 100.00 |
| The oil product total amount | 13.21 | 13.29 | 13.22 | 13.21 |
Annotate: in table 2-table 3, the oil product total amount refers to C
6H
6O+C
6H
6O
2The amount of+petroleum naphtha+middle oil+heavy oil
Table 4
From the results shown in Table 4, adopt method provided by the invention can effectively realize oily water separation in raw gas and raw gas, thereby effectively solve the oily(waste)water problem, and Comparative Examples 1 and Comparative Examples 2 temperature due to quenching oil is too low and too high respectively, W/O content after separation is higher, in water, oil-contg is higher, can not realize well oily water separation, thereby can not solve the oily(waste)water problem.This shows, can the temperature of quenching oil and duration of contact be the key points that solve the oily(waste)water problem.
Claims (10)
1. treatment process that contains the gas mixture of tar, this gas mixture that contains tar contains carbon monoxide, hydrogen, methane, carbonic acid gas, tar and water, and the method comprises the following steps:
(1) the described gas mixture that contains tar is contacted with organic solvent, the condition of contact comprises that the temperature of organic solvent is 70-200 ℃, and the time is 10 seconds to 120 seconds, obtains the first gaseous product and the first liquid product;
(2) isolate the first liquid product;
(3) described the first gaseous product is cooling, obtain purified gas and the second liquid product, isolate the second liquid product.
2. method according to claim 1, wherein, the condition that the described gas mixture that contains tar contacts with organic solvent comprises that the temperature of organic solvent is 80-180 ℃, the time is 10-100 second.
3. method according to claim 1 and 2, wherein, the described temperature that contains the gas mixture of tar is 150-750 ℃, pressure is the 2-6 MPa, the consumption of described organic solvent be the described gas mixture weight that contains tar 1-15 doubly.
4. method according to claim 3, wherein, the described temperature that contains the gas mixture of tar is 250-650 ℃, pressure is the 2-4 MPa, the consumption of described organic solvent be the described gas mixture weight that contains tar 1-5 doubly.
5. method according to claim 3, wherein, in the described gas mixture that contains tar, the content of water is the 10-60 % by weight, the content of tar is the 0.1-20 % by weight of the total amount of described outside the dewatering gas mixture that contains tar.
6. method according to claim 1 and 2, wherein, the described temperature that contains the gas mixture of tar is 80-200 ℃, pressure is the 0.08-0.3 MPa, the consumption of described organic solvent be the described gas mixture weight that contains tar 0.5-5 doubly.
7. method according to claim 6, wherein, the described temperature that contains the gas mixture of tar is 90-180 ℃, pressure is the 0.1-0.13 MPa, the consumption of described organic solvent be the described gas mixture that contains tar weight 1-3 doubly.
8. method according to claim 6, wherein, in the described gas mixture that contains tar, the content of tar is the 1-25 % by weight of the total amount of described outside the dewatering gas mixture that contains tar, the content of water is the 1-30 % by weight.
9. method according to claim 1, wherein, the method also comprises carries out oily water separation with the second liquid product.
10. method according to claim 1, wherein, described organic solvent is that boiling range is one or more in coal tar hydrocracking tail oil, diesel oil and the wax oil of 180-500 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4286971A (en) * | 1979-10-05 | 1981-09-01 | Bethlehem Steel Corporation | Removal of naphthalene from recirculated wash oil |
| CN1043334A (en) * | 1988-12-14 | 1990-06-27 | 克鲁普科普斯有限公司 | From the coal gas of partial oxidation, remove the method for hydrogen sulfide |
| US6312505B1 (en) * | 1999-11-19 | 2001-11-06 | Energy Process Technologies, Inc. | Particulate and aerosol remover |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4286971A (en) * | 1979-10-05 | 1981-09-01 | Bethlehem Steel Corporation | Removal of naphthalene from recirculated wash oil |
| CN1043334A (en) * | 1988-12-14 | 1990-06-27 | 克鲁普科普斯有限公司 | From the coal gas of partial oxidation, remove the method for hydrogen sulfide |
| US6312505B1 (en) * | 1999-11-19 | 2001-11-06 | Energy Process Technologies, Inc. | Particulate and aerosol remover |
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