CN109097085A - The pretreated method of coal tar - Google Patents
The pretreated method of coal tar Download PDFInfo
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- CN109097085A CN109097085A CN201710491707.0A CN201710491707A CN109097085A CN 109097085 A CN109097085 A CN 109097085A CN 201710491707 A CN201710491707 A CN 201710491707A CN 109097085 A CN109097085 A CN 109097085A
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- coal tar
- water
- demulsifier
- processing
- mixture
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C1/00—Working-up tar
- C10C1/02—Removal of water
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C1/00—Working-up tar
- C10C1/20—Refining by chemical means inorganic or organic compounds
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 carried out 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
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 into
Row heating treatment, the mixture after then will heat up are supplied into closed container, are dropped after the pressure of closed container is stablized
Pressure is handled, and in the treatment process carried out in a sealed container, the pressure reduction of closed container causes the coal tar in it to mix
Objects system sharply expands, and the water droplet in water-in-oil emulsion expands therewith, and the film-strength of oil-water interfaces substantially weakens, in conjunction with demulsification
It is easy to gather simultaneously, so that coal oil mixture system gravitational settling in closed container is for a period of time after the effect water droplet collision of agent
Water-oil separating can be achieved, while the impurity such as remaining metal, ash content are also removed with water phase, can obtain qualified purification coal tar
Oil.
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 subjected to heating treatment, the mixture that processing obtains then is will heat up and supplies
To 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.
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. is then combined using physics demulsification with chemical method, by the mixture of coal tar, water, demulsifier and metal remover
Heating treatment is carried out, the mixture that processing obtains then is will heat up and supplies into the dehydrator with relief valve, device to be drained off
Pressure successively carries out decompression processing and gravitational settling processing after stablizing, can be realized emulsified water break milk separation, further remove coal
Emulsified water and residual metal impurity in tar etc., obtained purification coal tar moisture content is low, and metal, content of ashes are low, can
Meet 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 carries out heating treatment, then will heat up the mixture that processing obtains and supplies into closed container, to closed
The pressure of container carries out decompression processing after stablizing, then the product that decompression is handled carries out gravitational settling processing.
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 10-300mg, further preferably 30-200mg.
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 1-5:1, further preferably
2-4:1.That is, the ratio of the integral molar quantity of iron and calcium is 1-5:1 in the mole and coal tar of metal remover, further preferably
2-4:1.
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, for by the specific embodiment of mixture progress heating treatment, there is no particular limitation,
It can be various methods commonly used in the art, as long as can control the temperature of the mixture at 110-180 DEG C, preferably
120-160 DEG C.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 0.25-3h, further
Preferably 0.5-2h.
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 2h is set, primary purifying coal tar is obtained；By primary purifying coal tar, demulsifier AE10071, (purchased from Shandong, Bin Hua group has
Responsible company is limited, similarly hereinafter) and the mixing of metal remover dimethylphosphite, relative to 1L coal tar raw material, the additional amount of demulsifier
For 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, and gained is mixed
Object exchanges heat through heat exchanger to 130 DEG C, is then supplied in the dehydrator with relief valve, closes inlet valve and relief valve, to de-
After pressure in hydrophone is stablized, open relief valve pressure release, gas enters condenser and carries out condensation separation processing, obtain 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, by the material gravity in dehydrator
Settle 1h carry out water-oil separating, be purified coal tar and the first water phase, will purification coal tar and light oil merge after supply to
In subsequent plus hydrogen made fuel oil technique, sewage disposal system will be drained into outside the first water phase, the second water phase is used for primary purifying
Coal tar preparation process is recycled.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 3h, 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
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, and gained mixture is passed through
Heat exchanger exchanges heat to 120 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
2h carries out water-oil separating, is purified coal tar and the first water phase, supplies after purification coal tar and light oil are merged to subsequent
Plus in hydrogen made fuel oil technique, sewage disposal system will be drained into outside the first water phase, the second water phase is used for primary purifying coal tar
Oily preparation process 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
150mg, the ratio of the integral molar quantity of iron and calcium is 4:1 in the mole and coal tar raw material of metal remover, by gained mixture
It exchanges heat through heat exchanger to 160 DEG C, is then supplied in the dehydrator with relief valve, close inlet valve and relief valve, it is to be drained off
After pressure in device is stablized, relief valve pressure release is opened, gas enters condenser and carries out condensation separation processing, obtains light oil and the
Two water phases；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 sunk
Drop 0.5h carry out water-oil separating, be purified coal tar and the first water phase, will purification coal tar and light oil merge after supply to
In subsequent plus hydrogen made fuel oil technique, sewage disposal system will be drained into outside the first water phase, the second water phase is used for primary purifying
Coal tar preparation process 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, by the mixture of primary purifying coal tar, demulsifier and metal remover
It exchanges heat through heat exchanger to 110 DEG C.The property for purifying coal tar is as shown in table 2.
Embodiment 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 180 DEG C.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 0.25h.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 3h.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 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.Gained is mixed
Object exchanges heat through heat exchanger to 130 DEG C, is then supplied in the dehydrator with relief valve, closes inlet valve and relief valve, to de-
After pressure in hydrophone is stablized, open relief valve pressure release, gas enters condenser and carries out condensation separation processing, obtain 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, by the material gravity in dehydrator
Settle 1h carry out water-oil separating, be purified coal tar and the first water phase, will purification coal tar and light oil merge after supply to
In subsequent plus hydrogen made fuel oil technique.Wherein, 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 200mg, the mole and coal tar of metal remover
The ratio of the integral molar quantity of iron and calcium is 5:1 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, 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 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, 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.
Table 2
| W (ash content)/% | W (iron)/(μ g/g) | W (calcium)/(μ g/g) | W (sodium)/(μ g/g) | W (water)/% | |
| Embodiment 1 | 0.006 | 6.8 | 8.6 | 1.5 | 0.25 |
| Embodiment 2 | 0.01 | 8.9 | 10.7 | 2.1 | 0.33 |
| Embodiment 3 | 0.007 | 7.5 | 8.8 | 2.2 | 0.28 |
| Embodiment 4 | 0.012 | 12.4 | 17.6 | 2.0 | 0.38 |
| Embodiment 5 | 0.009 | 9.8 | 12.6 | 2.2 | 0.26 |
| Embodiment 6 | 0.011 | 14.1 | 18.6 | 2.6 | 0.48 |
| Embodiment 7 | 0.008 | 7.0 | 8.7 | 1.6 | 0.26 |
| Embodiment 8 | 0.012 | 16.6 | 18.8 | 3.1 | 0.45 |
| Embodiment 9 | 0.008 | 10.2 | 10.5 | 2.0 | 0.36 |
| Comparative example 1 | 0.018 | 36.2 | 48.8 | 5.4 | 1.38 |
| Comparative example 2 | 0.026 | 46.5 | 59.8 | 7.8 | 4.25 |
| Comparative example 3 | 0.022 | 40.2 | 49.5 | 7.2 | 3.66 |
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 0.5-2h, 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 (10)
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 carries out heating treatment, then will heat up the mixture that processing obtains and supplies into closed container, to closed container
Pressure stablize after carry out decompression processing, then the product that decompression is handled carries out gravitational settling processing.
2. according to the method described in claim 1, wherein, the temperature for the mixture that heating treatment obtains is 110-180 DEG C, preferably
It is 120-160 DEG C；
Preferably, the heating treatment is heat exchange processing.
3. method according to claim 1 or 2, 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, the additional amount of demulsifier
For 10-300mg；For coal tar with the total moles meter of iron in coal tar and calcium, the molar ratio of metal remover and coal tar is 1-5:
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.
4. method described in any one of -3 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。
5. method described in any one of -4 according to claim 1, wherein the condition of the decompression processing includes: will be closed
The pressure of container is down to normal pressure.
6. according to the method described in claim 5, 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.
7. method described in any one of -6 according to claim 1, wherein when the condition of the gravitational settling processing includes:
Between be 0.25-3h, preferably 0.5-2h.
8. method according to any one of claims 1-7, wherein this method further include: handle gravitational settling
The oil arrived is mutually supplied to hydrotreating.
9. according to the method described in claim 6, 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.
10. method described in any one of -9 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113652255A (en) * | 2021-08-23 | 2021-11-16 | 内江市博威能源有限公司 | Medicament feeding device for coal tar recovery and use method thereof |
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