CN109097086A - The pretreated method of coal tar - Google Patents

The pretreated method of coal tar Download PDF

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Publication number
CN109097086A
CN109097086A CN201710491706.6A CN201710491706A CN109097086A CN 109097086 A CN109097086 A CN 109097086A CN 201710491706 A CN201710491706 A CN 201710491706A CN 109097086 A CN109097086 A CN 109097086A
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coal tar
water
demulsifier
mixture
processing
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CN109097086B (en
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沈明欢
李本高
于丽
王振宇
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10CWORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C1/00Working-up tar
    • C10C1/20Refining by chemical means inorganic or organic compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10CWORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C1/00Working-up tar
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10CWORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C1/00Working-up tar
    • C10C1/02Removal of water

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The present invention relates to the field of deep of coal tar, disclose a kind of pretreated method of coal tar, this method comprises: the mixture of coal tar, water, demulsifier and metal remover is successively carried out ultrasonication and heating treatment, then it will heat up the mixture that processing obtains to supply into closed container, decompression processing is carried out after the pressure of closed container is stablized, then the product that decompression is handled carries out gravitational settling processing.Method and process condition of the invention mitigates, equipment is simple, dosing is low, flexible operation, and obtained purification coal tar moisture content is low, and metal, content of ashes are low, can satisfy the requirement of follow-up hydrogenation treatment process.

Description

The pretreated method of coal tar
Technical field
The present invention relates to the field of deep of coal tar, and in particular to a kind of pretreated method of coal tar.
Background technique
Coal tar is a kind of with specific stimulation smell, black or dark brown, viscosity of the larger liquid product, generally It is generated during coal carbonization, gasification etc., coal is different, and pyrolytic process is different, and generated coal tar composition and property are deposited In larger difference.Currently, coal tar processing utilization ways mainly have following manner: production is extracted the chemical industry such as phenol, refined naphthalene, anthraquinone and is produced Product;It produces based on the pitches deep processings such as needle coke, high class pavement pitch;It directly burns as fuel oil;Using hydrofinishing or The technique of hydro-upgrading produces clean fuel oil.Wherein producing clean fuel oil by hydrogenation of coal tar technique is the environmental protection benefit of coal tar It is the hot spot technique during coal tar processing utilizes, but there are many more technology hardly possiblies for the technique with an extraordinary approach is provided Point needs perfect.Since moisture, inorganic salts, metal impurities content are higher in coal tar raw material, follow-up hydrogenation will be caused to handle A series of problems, such as middle corrosive pipeline, reactor plugs, catalyst poisoning and petrol and diesel oil yield decline, wherein metal is mainly iron Calcium sodium content is high, these metals of hydrogenation process can be deposited on catalyst surface, and less inside entrance catalyst granules, causes Catalyst bed pressure drop rises quickly to which to cause device shorter operation cycle in hydrogenation plant operational process, therefore coal tar adds Raw material must be dehydrated before hydrogen modification, demetalization, the pretreatment such as de-ash.
The pretreated method of coal tar is more, a kind of method that patent CN101838549B describes solvent fractional extraction, Soluble matter and impure extraction insoluble matter are isolated, using soluble matter as the charging of coal tar hydrogenation modification device, this method Need to consume a large amount of solvent, recycled solvent energy consumption is higher;Patent CN103642521B uses slurry bed system hydrogenator Raw material is pre-processed, subsequently into fixed bed hydrogenation reactor, the program has good metal removal effect, it is ensured that main to add The long-term operation of hydrogen production device, but complex process, equipment investment are big;Patent application CN105713658A discloses a kind of coal tar Pretreating process, after quantitative pharmacy and water mixing is added, 60-90 DEG C is centrifuged, and is then heated to 90-140 DEG C of entrance Electrical desalter processing, although electro-desalting pretreating process uses extensively in oil processing unit, technology maturation, not with crude oil Together, coal tar oil component is more complicated, electric conductivity itself is strong, easily leads to electric pole short circuit, breakdown, and grease does not have density contrast or difference It is worth very little, sedimentation separation is difficult in electrical desalter, therefore electric desalting apparatus need to be individually designed according to the progress of the property of coal tar, In addition, the centrifuge separation that is related to of the technique there are treating capacities it is small, equipment investment is big, and operating cost is high the problems such as.
Summary of the invention
The purpose of the invention is to overcome the above problem of the existing technology, a kind of pretreated side of coal tar is provided Method, this method process conditions mitigate, equipment is simple, dosing is low, flexible operation, and obtained purification coal tar moisture content Low, metal, content of ashes are low, can satisfy the requirement of follow-up hydrogenation treatment process.
The present inventor has been surprisingly found that under study for action, by the mixture of coal tar, water, demulsifier and metal remover according to Secondary progress ultrasonication and heating treatment, ultrasonication process are mainly acted on by two aspects: on the one hand can will be formed multiple Miscellaneous coal tar oil systems homogenize, and promote the interaction of medicament and coal tar, and being conducive to subsequent process, (closed container is dehydrated Device) it is further processed, on the other hand promote raw material to activate by ultrasonic heat effect and displacement effect, emulsion water droplet is easy to touch Hit aggregation, strength reduction the effects of interfacial activity substance such as solid impurity, colloid, asphalitine reduces demulsifier dosage, contracting The short heat sink drop residence time improves coal tar pretreating effect.Then it will heat up the coal oil mixture system that processing obtains to supply To into closed container, decompression processing is carried out after the pressure of closed container is stablized, this carried out in a sealed container is processed Cheng Zhong, the pressure reduction of closed container cause the coal oil mixture system in it sharply to expand, the water in water-in-oil emulsion Drop expands therewith, and the film-strength of oil-water interfaces substantially weakens, and is easy to gather simultaneously, so that coal after the effect water droplet collision in conjunction with demulsifier Water-oil separating, while the metal of remnants, ash can be realized in blended tars system gravitational settling in closed container for a period of time Divide equal impurity also to remove with water phase, qualified purification coal tar can be obtained.
Therefore, to achieve the goals above, the present invention provides a kind of pretreated methods of coal tar, this method comprises: The mixture of coal tar, water, demulsifier and metal remover is successively subjected to ultrasonication and heating treatment, then will heat up place It manages obtained mixture to supply into closed container, carries out decompression processing after the pressure of closed container is stablized, then will be at decompression It manages obtained product and carries out gravitational settling processing.
The present invention is directed to the difficult point of coal tar hydrogenation process, provides a kind of pretreated method of coal tar, for it is a kind of from The method that the impurity such as water, metal, ash content are removed in coal tar, this method can carry out the coal tar that grease difficulty separates good Pretreatment, and this method process conditions mitigate, equipment is simple, dosing is low, flexible operation, and obtained purification coal tar contains Water rate is low, and metal, content of ashes are low, can satisfy the requirement of follow-up hydrogenation treatment process, provides conjunction for follow-up hydrogenation treatment process The coal tar raw material of lattice, it is ensured that the long-period stable operation of hydrogenation plant is easy to commercial introduction application, before having good application Scape.
According to a preferred embodiment of the present invention, this method uses water-washing process+settle and separate processing (will first Coal tar and water mixing, carry out settle and separate processing, obtain primary purifying coal tar, then by primary purifying coal tar, demulsifier Mixed with metal remover), most of free water and partial salts, water-soluble metal, ash content and solid are removed after settle and separate Impurity etc. reduces the difficulty of subsequent decompression dehydration, adopts then in conjunction with the synergistic effect of the physical action of ultrasonic wave and chemical agent Emulsified water and residual metal impurity in coal tar etc. are further removed with the mode that pressure release is handled, obtained purification coal tar contains Water rate is low, and metal, content of ashes are low, can satisfy the requirement of follow-up hydrogenation treatment process.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of pretreated methods of coal tar, this method comprises: by coal tar, water, demulsifier and taking off The mixture of metal agent successively carries out ultrasonication and heating treatment, then will heat up the mixture that processing obtains and supplies to close It closes in container, decompression processing is carried out after the pressure of closed container is stablized, then the product that decompression is handled is subjected to gravity and is sunk Drop processing.
In the case of process of the present invention it is preferred, the condition of ultrasonication includes: that ultrasonic frequency is 20-40kHz, The sound intensity is 2-8W/cm2, ultrasonic time 3-30min.
In the case of process of the present invention it is preferred, the coal tar, water, demulsifier and metal remover mixture in, with On the basis of the weight of coal tar, the additional amount of water is 5-30 weight %.
In the case of process of the present invention it is preferred, the coal tar, water, demulsifier and metal remover mixture in, phase For 1L coal tar, the additional amount of demulsifier is 1-200mg, further preferably 10-100mg.
In the case of process of the present invention it is preferred, the coal tar, water, demulsifier and metal remover mixture in, coal Tar is with the total moles meter of iron in coal tar and calcium, and the molar ratio of metal remover and coal tar is 0.5-4:1, further preferably For 1-3:1.That is, the ratio of the integral molar quantity of iron and calcium is 0.5-4:1 in the mole and coal tar of metal remover, it is further excellent It is selected as 1-3:1.
Preferably, the water is at least one of purified water, including distilled water, deionized water and softened water.
Preferably, the demulsifier is polyether demulsification agent (for polyethers demulsifier for water in oil emulsion), further preferably Ground, polyethers demulsifier are branch shape polyethers demulsifier;It is further preferred that polyethers demulsifier is to be with polyethylene polyamine The polyoxypropylene of initiator, polyoxyethylene blocks polyethers (including but not limited to AE series, AP series demulsifier), with phenolic resin And/or phenol amine resin is the polyoxypropylene of initiator, polyoxyethylene blocks polyethers (including but not limited to F3111 series, TA1031 Series, ST14 series demulsifier) and the block polyether that is modified using toluene di-isocyanate(TDI) as chain extender or unsaturated monomer In (including but not limited to BCO1912 series, POI2420 series, SD-903 series, M-501 series, GD9909 series demulsifier) At least one.Wherein it is possible to be selected according to type of the property of coal tar to demulsifier, selection method is this field skill Known to art personnel, details are not described herein.
Preferably, the metal remover is organic acid and/or organic acid derivatives, it is further preferred that the organic acid For at least one of oxalic acid, maleic acid, phosphorous acid and 1-hydroxy ethylidene-1,1-diphosphonic acid, the organic acid derivatives be maleic anhydride, At least one of dimethylphosphite and Trimethyl phosphite.Aforementioned metal remover has good calcium, iron removal effect.
In the case of process of the present invention it is preferred, the coal tar is prepared using one or both of following two mode Oil, water, demulsifier and metal remover mixture:
Mode 1: directly coal tar, water, demulsifier and metal remover are mixed;
Mode 2: first mixing coal tar and water, carries out settle and separate processing, obtains primary purifying coal tar, then will be primary Purify coal tar, demulsifier and metal remover mixing.
For depressant consumption, coal tar pretreating effect, preferably mode 2 are further increased, it is further preferred that mode In 2, settle and separate processing condition include: dwell temperature be 70-90 DEG C, time of repose 0.5-4h, still more preferably for 1-2h。
Preferably, in mode 2, on the basis of the weight of coal tar, the additional amount of water is 5-30 weight %.
It will be understood by those skilled in the art that being sufficiently mixed after can preheating coal tar raw material with water in mode 2 Into settling tank, water-oil separating is carried out in 70-90 DEG C of sedimentation a period of time, most of free water and contamination precipitation object can be removed Deng obtaining primary purifying coal tar.
In method of the invention, in mode 1, the mixing of coal tar, water, demulsifier and metal remover can be mixed by static state The mode of clutch mixing carries out;In mode 2, the mixing of coal tar and water can carry out in such a way that static mixer mixes, Primary purifying coal tar, demulsifier and metal remover mixing can also carry out in such a way that static mixer mixes.
In method of the invention, the present inventor has found under study for action, the temperature for the mixture that heating treatment obtains The steady pressure of closed container is related before handling decompression, and has a significant impact to the pretreating effect of coal tar, in order to significant The pretreating effect for improving coal tar, under preferable case, the temperature for the mixture that heating treatment obtains is 110-180 DEG C, into one Preferably 120-160 DEG C of step.
In method of the invention, it can be this field that for the specific embodiment of heating treatment, there is no particular limitation Common various methods, as long as the temperature that can will heat up rear mixture is controlled at 110-180 DEG C, preferably 120-160 DEG C i.e. It can.Under preferable case, heating treatment is heat exchange processing.
In the case of process of the present invention it is preferred, the condition for being depressured processing includes: to be down to the pressure of closed container often Pressure.It will be understood by those skilled in the art that normal pressure refers to the standard atmospheric pressure in coal tar pretreatment location.
In method of the invention, for closed container, there is no particular limitation, can for common various in this field The closed container that the air pressure of container is reduced, under preferable case, closed container is the dehydrator with relief valve, is depressured processing Process is controlled by relief valve.
In method of the invention, according to the processing capacity of the oil mass of coal tar and dehydrator, dehydrator can use more It is used in parallel, it is therefore preferable that in the case of, the mixture that processing obtains can be will heat up and supplied at least two bands used in parallel Have in the dehydrator of relief valve.
In method of the invention, the coal oil mixture that will heat up processing supplies into closed container and carries out decompression processing Embodiment may include: that mixture after will heat up is supplied to dehydrator, after reaching dehydrator treating capacity, close inlet valve And relief valve, after the pressure of device to be drained off is stablized, relief valve is opened by the pressure of dehydrator and is down to normal pressure, is then shut off pressure release Valve.It will be understood by those skilled in the art that mixture after heating reaches required temperature, is supplied into dehydrator, close Inlet valve and relief valve, temperature and composition based on mixture, the pressure in dehydrator can rise and eventually keep stable Pressure quickly opens relief valve after the pressure of device to be drained off is stablized, and the pressure reduction in dehydrator takes off up to stablizing to normal pressure Coal tar oil systems inside hydrophone sharply expand, and the water droplet in water-in-oil emulsion expands therewith, and oil-water interfaces film-strength is substantially Weaken, is easy to gather after the effect water droplet collision in conjunction with demulsifier simultaneously, grease point can be realized in sedimentation a period of time in dehydrator From, while the impurity such as remaining metal, ash content are also removed with water phase, obtain qualified purification coal tar.
In the case of process of the present invention it is preferred, gravitational settling processing condition include: the time be 0.1-2h, further Preferably 0.2-1h.
In the case of process of the present invention it is preferred, this method further include: the oily phase for handling gravitational settling is (i.e. net Change coal tar) it supplies to hydrotreating (as added the processing of hydrogen made fuel oil), the water phase that gravitational settling is handled is drained into dirt outside Water treatment system.
In the case of process of the present invention it is preferred, this method further include: condense and separate the gas that relief valve is discharged Processing, and mutually supply will condense and separate the oil that condensation separation is handled to hydrotreating (such as plus the processing of hydrogen made fuel oil) It handles obtained water phase and is used to prepare the mixture of the coal tar, water, demulsifier and metal remover to be recycled. Since the oily phasor that condensation separation is handled is seldom, it is therefore preferable that oil phase and gravitational settling that condensation separation is handled It handles and is supplied after obtained oil mutually merges to follow-up hydrogenation processing;Since the water phase that condensation separation is handled is miscellaneous without metal etc. Matter, thus can be recycled.
Method of the invention is applicable to the pretreatment of the coal tar of grease difficulty separation, under preferable case, the coal tar In, the content of ash content is 0.03-0.3 weight %, and the content of colloid is 10-60 weight %, further preferably 20-50 weight Measure %;The content of asphalitine is 2-50 weight %, further preferably 10-40 weight %.
Embodiment
The present invention will be described in detail by way of examples below, but is not intended to limit the present invention.Following embodiment In comparative example, if not otherwise specified, each reagent is commercially available, and each method used is method commonly used in the art.
The measuring method of content of ashes in coal tar are as follows: GB/T 508-1985.
The measuring method of content of impurities in coal tar are as follows: GB/T 511-2010.
The measuring method of gum level in coal tar are as follows: SY/T 7550-2012.
The measuring method of coal tar studies on asphaltene content are as follows: SY/T 7550-2012.
The measuring method of metallic iron, calcium, sodium content in coal tar are as follows: ASTM D4951-2014.
The measuring method of water content in coal tar are as follows: GB/T 2288-2008.
The property for carrying out pretreated coal tar raw material is as shown in table 1.
Table 1
Embodiment 1
The present embodiment is for illustrating the pretreated method of coal tar of the invention.
Coal tar raw material and distilled water are mixed, on the basis of the weight of coal tar raw material, the dosage of distilled water is 20 weights % is measured, the mixture of coal tar raw material and distilled water is exchanged heat through heat exchanger to 80 DEG C, and is supplied quiet at 80 DEG C into settling tank Separation 1.5h is set, primary purifying coal tar is obtained;Primary purifying coal tar, demulsifier AE10071 (are purchased from Shandong Bin Hua group Co., Ltd, similarly hereinafter) and the mixing of metal remover dimethylphosphite, relative to 1L coal tar raw material, the addition of demulsifier Amount is 50mg, and the ratio of the integral molar quantity of iron and calcium is 2:1 in the mole and coal tar raw material of metal remover, and gained is mixed Object supplies to ultrasound reactor and carries out ultrasonication, and the condition of ultrasonication includes: that ultrasonic frequency is 30kHz, sound It is by force 5W/cm2, ultrasonic time 10min;Then the mixture that ultrasonication obtains is exchanged heat through heat exchanger to 130 DEG C, then Supply closes inlet valve and relief valve into the dehydrator with relief valve, after the pressure in device to be drained off is stablized, opens pressure release Valve pressure release, gas enter condenser and carry out condensation separation processing, obtain light oil and the second water phase;Pressure drop in device to be drained off Relief valve is closed after to normal pressure and pressure stabilization, the material gravity sedimentation 0.5h in dehydrator is subjected to water-oil separating, is obtained net Change coal tar and the first water phase, supply adds in hydrogen made fuel oil technique to subsequent after purification coal tar and light oil are merged, Sewage disposal system will be drained into outside first water phase, and the second water phase is used to primary purifying coal tar preparation process carry out circulation making With.Wherein, the property for purifying coal tar is as shown in table 2.
Embodiment 2
The present embodiment is for illustrating the pretreated method of coal tar of the invention.
Coal tar raw material and deionized water are mixed, on the basis of the weight of coal tar raw material, the dosage of deionized water is 5 Weight % exchanges heat the mixture of coal tar raw material and deionized water to 70 DEG C through heat exchanger, and supplies into settling tank 70 DEG C settle and separate 2h, obtains primary purifying coal tar;Primary purifying coal tar, demulsifier TA1031 (are purchased from Shandong Bin Huaji Co., Ltd of group) and the mixing of metal remover maleic anhydride, relative to 1L coal tar raw material, the additional amount of demulsifier is 30mg, the ratio of the integral molar quantity of iron and calcium is 1:1 in the mole and coal tar raw material of metal remover, and gained mixture is supplied Ultrasonication is carried out to ultrasound reactor, the condition of ultrasonication includes: that ultrasonic frequency is 40kHz, and the sound intensity is 3W/cm2, ultrasonic time 15min;Then the mixture that ultrasonication obtains is exchanged heat through heat exchanger to 120 DEG C, is resupplied Into the dehydrator with relief valve, inlet valve and relief valve are closed, after the pressure in device to be drained off is stablized, relief valve is opened and lets out Pressure, gas enter condenser and carry out condensation separation processing, obtain light oil and the second water phase;Pressure in device to be drained off is down to often Pressure and pressure close relief valve after stablizing, and the material gravity sedimentation 1h in dehydrator is carried out water-oil separating, is purified coal tar Oil and the first water phase, supply is into subsequent plus hydrogen made fuel oil technique after purification coal tar and light oil are merged, by first Sewage disposal system is drained into outside water phase, the second water phase is used for primary purifying coal tar preparation process and is recycled.Wherein, The property for purifying coal tar is as shown in table 2.
Embodiment 3
The present embodiment is for illustrating the pretreated method of coal tar of the invention.
Coal tar raw material and softened water are mixed, on the basis of the weight of coal tar raw material, the dosage of softened water is 30 weights % is measured, the mixture of coal tar raw material and softened water is exchanged heat through heat exchanger to 90 DEG C, and is supplied quiet at 90 DEG C into settling tank Separation 1h is set, primary purifying coal tar is obtained;By primary purifying coal tar, demulsifier AE10071, (purchased from Shandong, Bin Hua group has Limit responsible company) and the mixing of metal remover 1-hydroxy ethylidene-1,1-diphosphonic acid, relative to 1L coal tar raw material, the additional amount of demulsifier is 100mg, the ratio of the integral molar quantity of iron and calcium is 3:1 in the mole and coal tar raw material of metal remover, by gained mixture Supply to ultrasound reactor carries out ultrasonication, and the condition of ultrasonication includes: that ultrasonic frequency is 20kHz, the sound intensity For 8W/cm2, ultrasonic time 30min;Then the mixture that ultrasonication obtains is exchanged heat through heat exchanger to 160 DEG C, then supplied To inlet valve and relief valve into the dehydrator with relief valve, is closed, after the pressure in device to be drained off is stablized, relief valve is opened Pressure release, gas enter condenser and carry out condensation separation processing, obtain light oil and the second water phase;Pressure in device to be drained off is down to Normal pressure and pressure close relief valve after stablizing, and the material gravity sedimentation 0.2h in dehydrator is carried out water-oil separating, is purified Coal tar and the first water phase, supply, will into subsequent plus hydrogen made fuel oil technique after purification coal tar and light oil are merged Sewage disposal system is drained into outside first water phase, the second water phase is used for primary purifying coal tar preparation process and is recycled. Wherein, the property for purifying coal tar is as shown in table 2.
Embodiment 4
According to the method for embodiment 1, unlike, the mixture that ultrasonication obtains is exchanged heat through heat exchanger to 110 ℃.The property for purifying coal tar is as shown in table 2.
Embodiment 5
According to the method for embodiment 1, unlike, the mixture that ultrasonication obtains is exchanged heat through heat exchanger to 180 ℃.The property for purifying coal tar is as shown in table 2.
Embodiment 6
According to the method for embodiment 1, unlike, the time of the material gravity sedimentation in dehydrator is 0.1h.Purify coal The property of tar is as shown in table 2.
Embodiment 7
According to the method for embodiment 1, unlike, the time of the material gravity sedimentation in dehydrator is 2h.Purify coal tar The property of oil is as shown in table 2.
Embodiment 8
According to the method for embodiment 1, unlike, coal tar raw material, distilled water, demulsifier and metal remover mixture Preparation method it is different, specifically, this method is as follows:
Coal tar raw material, distilled water, demulsifier AE10071 and metal remover dimethylphosphite are mixed, wherein with coal On the basis of the weight of tar stock, the dosage of distilled water is 20 weight %, relative to 1L coal tar raw material, the additional amount of demulsifier For 50mg, the ratio of the integral molar quantity of iron and calcium is 2:1 in the mole and coal tar raw material of metal remover.By gained mixture Supply to ultrasound reactor carries out ultrasonication, and the condition of ultrasonication includes: that ultrasonic frequency is 30kHz, the sound intensity For 5W/cm2, ultrasonic time 10min;Then the mixture that ultrasonication obtains is exchanged heat through heat exchanger to 130 DEG C, then supplied To inlet valve and relief valve into the dehydrator with relief valve, is closed, after the pressure in device to be drained off is stablized, relief valve is opened Pressure release, gas enter condenser and carry out condensation separation processing, obtain light oil and the second water phase;Pressure in device to be drained off is down to Normal pressure and pressure close relief valve after stablizing, and the material gravity sedimentation 0.5h in dehydrator is carried out water-oil separating, is purified Coal tar and the first water phase, supply is into subsequent plus hydrogen made fuel oil technique after purification coal tar and light oil are merged.Its In, the property for purifying coal tar is as shown in table 2.
Embodiment 9
According to the method for embodiment 8, the difference is that, demulsifier additional amount is 100mg, the mole and coal tar of metal remover The ratio of the integral molar quantity of iron and calcium is 4:1 in oily raw material.
Comparative example 1
According to the method for embodiment 1, unlike, primary purifying coal tar (being added without demulsifier and metal remover) is passed through Heat exchanger exchanges heat to 130 DEG C, is then supplied in the dehydrator with relief valve, closes inlet valve and relief valve, device to be drained off After interior pressure is stablized, relief valve pressure release is opened, gas enters condenser and carries out condensation separation processing, obtains light oil and second Water phase;Pressure in device to be drained off closes relief valve after being down to normal pressure and pressure stabilization, and the material gravity in dehydrator is settled 1h carries out water-oil separating, obtains oily phase and the first water phase.Wherein, the property of oily phase is as shown in table 2.
Comparative example 2
According to the method for embodiment 1, unlike, primary purifying coal tar (being added without demulsifier and metal remover) is supplied Ultrasonication is carried out to ultrasound reactor, the condition of ultrasonication includes: that ultrasonic frequency is 30kHz, and the sound intensity is 5W/cm2, ultrasonic time 10min;Then the product that ultrasonication obtains is exchanged heat through heat exchanger to 130 DEG C, resupply to In dehydrator with relief valve, inlet valve and relief valve are closed, after the pressure in device to be drained off is stablized, relief valve is opened and lets out Pressure, gas enter condenser and carry out condensation separation processing, obtain light oil and the second water phase;Pressure in device to be drained off is down to often Pressure and pressure close relief valve after stablizing, and the material gravity sedimentation 0.5h in dehydrator is carried out water-oil separating, obtain it is oily mutually and First water phase.Wherein, the property of oily phase is as shown in table 2.
Comparative example 3
According to the method for embodiment 1, unlike, by the mixture of primary purifying coal tar, demulsifier and metal remover It exchanges heat through heat exchanger to 130 DEG C, is then supplied in coal tar pretreatment tank, 130 DEG C of sedimentation 4h obtain oily phase and water phase.Its In, the property of oily phase is as shown in table 2.
Comparative example 4
According to the method for embodiment 1, unlike, the mixture that ultrasonication obtains is exchanged heat through heat exchanger to 130 DEG C, it resupplies into coal tar pretreatment tank, 130 DEG C of sedimentation 4h obtain oily phase and water phase.Wherein, the property of oily phase such as 2 institute of table Show.
Comparative example 5
According to the method for embodiment 1, unlike, by the mixture of primary purifying coal tar, demulsifier and metal remover It exchanges heat through heat exchanger to 130 DEG C, is then supplied in coal tar pretreatment tank, then 130 DEG C of sedimentation 3h will be mixed by heat exchanger It closes object and is cooled to 85 DEG C, 85 DEG C of mixture is supplied into coal tar oil tank, stand 4h, obtain oily phase and water phase.Wherein, oily The property of phase is as shown in table 2.
Comparative example 6
According to the method for embodiment 1, unlike, the mixture that ultrasonication obtains is exchanged heat through heat exchanger to 130 DEG C, it resupplies into coal tar pretreatment tank, then mixture is cooled to 85 DEG C by heat exchanger, by 85 by 130 DEG C of sedimentation 3h DEG C mixture supply into coal tar oil tank, stand 4h, obtain it is oily mutually and water phase.Wherein, the property of oily phase is as shown in table 2.
Table 2
W (ash content)/% W (iron)/(μ g/g) W (calcium)/(μ g/g) W (sodium)/(μ g/g) W (water)/%
Embodiment 1 0.003 3.8 4.6 0.5 0.15
Embodiment 2 0.006 5.5 5.8 1.1 0.18
Embodiment 3 0.005 4.9 5.2 0.6 0.18
Embodiment 4 0.008 7.8 8.5 1.2 0.22
Embodiment 5 0.009 6.6 6.2 0.8 0.20
Embodiment 6 0.008 8.5 7.8 1.5 0.30
Embodiment 7 0.004 3.9 4.8 0.6 0.16
Embodiment 8 0.010 9.8 11.0 1.5 0.35
Embodiment 9 0.007 6.8 8.8 0.6 0.17
Comparative example 1 0.018 36.2 48.8 5.4 1.38
Comparative example 2 0.012 22.5 30.8 2.5 0.78
Comparative example 3 0.026 46.5 59.8 7.8 4.25
Comparative example 4 0.018 36.1 42.2 4.0 3.05
Comparative example 5 0.022 40.2 49.5 7.2 3.66
Comparative example 6 0.014 30.8 38.7 4.2 2.58
It can be seen that the grease difficulty high for asphalitine and gum level by the result of table 1 and separate coal tar, using this The moisture content for the purification coal tar that the method for invention obtains is significant lower, and metal, content of ashes are also significant lower.
The result of embodiment 1 and embodiment 4-5 is compared it is found that the temperature for controlling the mixture that heating treatment obtains is At 120-160 DEG C, moisture content, tenor and the content of ashes of purification coal tar can be further decreased.
The result of embodiment 1 and embodiment 6-7 is compared it is found that when gravitational settling is handled as 0.2-1h, it can be further Moisture content, tenor and the content of ashes of purification coal tar are reduced, and can be improved treatment effeciency.
The result of embodiment 1 and embodiment 8-9 is compared it is found that preparing the mixed of coal tar, water, demulsifier and metal remover When closing object, first coal tar and water are mixed, carry out settle and separate processing, obtains primary purifying coal tar, then by primary purifying coal Tar, demulsifier and metal remover mixing, can not only depressant consumption, additionally it is possible to further decrease purification coal tar it is aqueous Rate, tenor and content of ashes.
Method of the invention, process conditions mitigate, equipment is simple, dosing is low, flexible operation, are suitable for grease difficulty point From coal tar pretreatment, and obtained purification coal tar moisture content is low, and metal, content of ashes are low, can satisfy it is subsequent plus The requirement of hydrogen treatment process.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to Protection scope of the present invention.

Claims (11)

1. a kind of pretreated method of coal tar, which is characterized in that this method comprises: by coal tar, water, demulsifier and demetalization The mixture of agent successively carries out ultrasonication and heating treatment, then will heat up the mixture that processing obtains and supplies to closed appearance In device, decompression processing is carried out after the pressure of closed container is stablized, then the product that decompression is handled carries out at gravitational settling Reason.
2. according to the method described in claim 1, wherein, the condition of the ultrasonication includes: that ultrasonic frequency is 20- 40kHz, sound intensity 2-8W/cm2, ultrasonic time 3-30min.
3. method according to claim 1 or 2, wherein the temperature for the mixture that heating treatment obtains is 110-180 DEG C, Preferably 120-160 DEG C;
Preferably, the heating treatment is heat exchange processing.
4. method described in any one of -3 according to claim 1, wherein the coal tar, water, demulsifier and metal remover Mixture in, on the basis of the weight of coal tar, the additional amount of water is 5-30 weight %;Relative to 1L coal tar, demulsifier Additional amount be 1-200mg;Coal tar is with the total moles meter of iron in coal tar and calcium, the molar ratio of metal remover and coal tar For 0.5-4:1;
Preferably, the demulsifier is polyether demulsification agent;
Preferably, the metal remover is organic acid and/or organic acid derivatives;
It is further preferred that the organic acid is at least one of oxalic acid, maleic acid, phosphorous acid and 1-hydroxy ethylidene-1,1-diphosphonic acid;
It is further preferred that the organic acid derivatives be maleic anhydride, dimethylphosphite and Trimethyl phosphite in extremely Few one kind.
5. method described in any one of -4 according to claim 1, wherein using one or both of following two mode Prepare the mixture of the coal tar, water, demulsifier and metal remover:
Mode 1: directly coal tar, water, demulsifier and metal remover are mixed;
Mode 2: first mixing coal tar and water, carries out settle and separate processing, obtains primary purifying coal tar, then by primary purifying Coal tar, demulsifier and metal remover mixing;
Preferably, in mode 2, it is 70-90 DEG C that the condition of the settle and separate processing, which includes: dwell temperature, and time of repose is 0.5-4h。
6. method described in any one of -5 according to claim 1, wherein the condition of the decompression processing includes: will be closed The pressure of container is down to normal pressure.
7. according to the method described in claim 6, wherein, the closed container is the dehydrator with relief valve, the decompression The process of processing is controlled by relief valve;
Preferably, it will heat up the mixture that processing obtains to supply at least two dehydrators with relief valve used in parallel In.
8. method according to any one of claims 1-7, wherein when the condition of the gravitational settling processing includes: Between be 0.1-2h, preferably 0.2-1h.
9. method described in any one of -8 according to claim 1, wherein this method further include: handle gravitational settling The oil arrived is mutually supplied to hydrotreating.
10. according to the method described in claim 7, wherein, this method further include: the gas that relief valve is discharged is subjected to condensation point From processing, and mutually to hydrotreating, the water phase that condensation separation is handled is used for the oil that condensation separation is handled for supply The mixture of the coal tar, water, demulsifier and metal remover is prepared to be recycled.
11. method described in any one of -10 according to claim 1, wherein in the coal tar, the content of ash content is 0.03-0.3 weight %, the content of colloid are 10-60 weight %, and the content of asphalitine is 2-50 weight %.
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