CN106582529B - A kind of biomass-residual oil is total to application of the coking active carbon in crude oil absorption desulfurization - Google Patents
A kind of biomass-residual oil is total to application of the coking active carbon in crude oil absorption desulfurization Download PDFInfo
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- CN106582529B CN106582529B CN201611235351.6A CN201611235351A CN106582529B CN 106582529 B CN106582529 B CN 106582529B CN 201611235351 A CN201611235351 A CN 201611235351A CN 106582529 B CN106582529 B CN 106582529B
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28076—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being more than 1.0 ml/g
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/06—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with moving sorbents or sorbents dispersed in the oil
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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Abstract
The present invention provides a kind of biomass-residual oil to be total to application of the coking active carbon in crude oil absorption desulfurization; biomass-the residual oil is total to coking active carbon and is obtained by the preparation method included the following steps: under inert gas protection; biomass and residual oil are subjected to co carbonization reaction, obtain total coking；Hydrophily pretreatment is successively carried out to total coking and except ash content pre-processes, obtains pretreated coking altogether；Under inert gas protection, pretreated coking altogether is roasted, obtains biology base Carbon Materials；Under inert gas protection, biology base carbon material and activator are subjected to priming reaction, obtain biomass-residual oil and is total to coking active carbon.The present invention prepares active carbon using biomass and residual oil as raw material, obtained active carbon just has high-specific surface area, high total pore volume, the activated carbon application can be obtained into preferable desulfurization effect in crude oil absorption desulfurization, and in the present invention active carbon raw material sources it is extensive, it is at low cost, it further reduced the cost of crude oil absorption desulfurization.
Description
Technical field
The present invention relates to a kind of technical field of active carbon desulfurization, in particular to a kind of biomass-residual oil is total to coking activity
Application of the charcoal in crude oil absorption desulfurization.
Background technique
In recent years, worse and worse, wherein heavy crude and high-sulphur crude are more and more for the crude quality of refinery's processing, oil
Sulfide in product can corrode process equipment, and cause catalyst poisoning in oil refining process.Therefore, enter refinery in crude oil
Pre- desulfurization is carried out before process equipment, the protection and two aspect of environmental protection for production equipment all have great importance, research hair
Exhibition has good prospects.Traditional hydrodesulfurization technology, although this problem can be solved to a certain extent, due to its reaction
Condition is harsh, at high cost, risk is big, and non-best choice.
Activated carbon adsorption desulfurization is a kind of new direct desulfurization method, has compared with hydrodesulfurization technology and does not need hydrogen
Gas, easy to operate, low expense, it is more environmentally friendly, can carry out at normal temperatures and pressures, and deep desulfuration can be used for.But it is industrial at present
Most widely used active carbon is active carbon from coal, and the specific surface area of active carbon from coal is not high, generally 500~1200m2/ g,
Absorption property is poor, be largely in low-quality active carbon, be not able to satisfy the needs in increasingly developed PETROLEUM PROCESSING field, and
And as increasingly scarcity, the price of coal of the enhancing of social environment consciousness and the energy gradually go up, the raw material of coal based activated carbon
It is very limited, preparation cost also gradually goes up.
Summary of the invention
In view of this, being total to coking active carbon it is an object of that present invention to provide a kind of biomass-residual oil adsorbs desulfurization in crude oil
In application, it is from a wealth of sources that biomass-residual oil is total to coking activated carbon raw material, at low cost, and the biomass-residual oil being prepared is total
Coking activity carbon activity height, specific surface area with higher and Kong Rong.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of biomass-residual oil to be total to application of the coking active carbon in crude oil absorption desulfurization, the life
Substance-residual oil is total to coking active carbon and is obtained by the preparation method included the following steps:
Under inert gas protection, biomass and residual oil are subjected to co carbonization reaction, obtain total coking；
Hydrophily pretreatment is successively carried out to the coking altogether and except ash content pre-processes, obtains pretreated coking altogether；
Under inert gas protection, by the pretreated coking roasting altogether, biology base Carbon Materials are obtained；
Under inert gas protection, the biology base carbon material and activator are subjected to priming reaction, obtain biomass-slag
The total coking active carbon of oil.
Preferably, the biomass is sawdust and/or Enteromorpha.
Preferably, the mass ratio of the biomass and residual oil is 0~0.5:1.
Preferably, the temperature of the co carbonization reaction is 400~500 DEG C；The time of the co carbonization reaction is 3~5h.
Preferably, the temperature of the roasting is 500~510 DEG C；The time of the roasting is 1~2h.
Preferably, the activator is the mixture of one or more of hydroxide and bicarbonate；The activation
The mass ratio of agent and biology base carbon material is 2~5:1.
Preferably, the temperature of the priming reaction is 800~805 DEG C；The time of the priming reaction is 1~2h.
Preferably, it is that transition metal support type biomass-residual oil is total to coking work that the biomass-residual oil, which is total to coking active carbon,
Property charcoal.
Preferably, the metal load type biomass-residual oil is total to coking active carbon by the preparation method that includes the following steps
It obtains:
Biomass-residual oil is total to after coking active carbon impregnates in transition metal salt solution to dry work after being impregnated
Property carbon；
By the activated carbon roasting after the dipping, transition metal load type active carbon is obtained.
Preferably, the dipping is double-steeping, comprising the following steps:
By biomass-residual oil be total to coking active carbon carried out in transition metal salt solution after the first dipping it is first dry, will
Active carbon after drying carries out the second dipping, the active carbon after being impregnated after the second drying in transition metal salt solution；Institute
The concentration for stating the first dipping and the transition metal salt solution in the second dipping is independently 0.5~0.7mol/L.
The present invention provides a kind of biomass-residual oil to be total to application of the coking active carbon in crude oil absorption desulfurization, the life
Substance-residual oil is total to coking active carbon and is obtained by the preparation method included the following steps: under inert gas protection, by biomass and
Residual oil carries out co carbonization reaction, obtains total coking；The coking altogether is successively carried out hydrophily pretreatment and removes ash content to pre-process,
Obtain pretreated coking altogether；Under inert gas protection, by the pretreated coking roasting altogether, biology base charcoal is obtained
Material；Under inert gas protection, the biology base carbon material and activator are subjected to priming reaction, obtain biomass-residual oil
Coking active carbon altogether.The present invention improves the type and quantity of oxygen-containing functional group in Carbon Materials using biomass for raw material, thus
Improve the activity of active carbon；Using biological burnt short texture, mechanical strength is low and the spy of petroleum coke compact structure, high mechanical strength
Point greatly improves active carbon specific surface area and total hole volume；And in the present invention active carbon raw material sources it is extensive, can not only increase
The preparation cost for adding economic benefit, reducing active carbon, additionally it is possible to reduce the waste discharges such as biomass and residual oil, it is dirty to reduce environment
Dye, the experimental results showed that, the specific surface area for the active carbon that preparation method provided by the invention obtains can achieve 2400m2/ g, always
Kong Rong can achieve 1.5m3/g.Biomass-residual oil is total to coking activated carbon application in crude oil absorption desulfurization, it can be further
Desulphurization cost is reduced, desulfuration efficiency is improved, promotes the development and progress of desulfurizing oil technology.
Detailed description of the invention
Fig. 1 is the electron scanning micrograph that biomass-residual oil prepared by the embodiment of the present invention 1 is total to coking active carbon；
Fig. 2 is the electron scanning micrograph that biomass-residual oil prepared by the embodiment of the present invention 2 is total to coking active carbon；
Fig. 3 is co carbonization reaction unit schematic diagram in the embodiment of the present invention；
In Fig. 3: 1- temperature controller, 2- inert gas inleting pipe, 3- heating furnace, 4- co carbonization reaction kettle, 5- delivery line, 6- liquid
Body receiver, 7- escape pipe, 8- ice-water bath container.
Fig. 4 is aobvious for the scanning electron that metal load type biomass-residual oil prepared by the embodiment of the present invention 6 is total to coking active carbon
Micro mirror photo.
Specific embodiment
The present invention provides a kind of biomass-residual oil to be total to application of the coking active carbon in crude oil absorption desulfurization, the life
Substance-residual oil is total to coking active carbon and is obtained by the preparation method included the following steps:
Under inert gas protection, biomass and residual oil are subjected to co carbonization reaction, obtain total coking；
Hydrophily pretreatment is successively carried out to the coking altogether and except ash content pre-processes, obtains pretreated coking altogether；
Under inert gas protection, by the pretreated coking roasting altogether, biology base Carbon Materials are obtained；
Under inert gas protection, the biology base carbon material and activator are subjected to priming reaction, obtain biomass-slag
The total coking active carbon of oil.
The present invention carries out co carbonization reaction under the conditions of inert gas shielding, by biomass and residual oil, obtains total coking.?
In the present invention, the biomass is preferably Enteromorpha and/or sawdust.
Enteromorpha is widely distributed in ocean, brackish water or rivers, and the Enteromorpha in the present invention directly passes through salvaging and obtains；This hair
It is bright preferably the obtained Enteromorpha of salvaging is pre-processed after as the raw material for preparing active carbon, the preferred packet of pretreatment
It includes: successively Enteromorpha being washed, dried and is ground.In the present invention, the washing is preferably water with detergent, the washing
Number be preferably 2~5 times, more preferably 3~4 times；The temperature of the drying is preferably 100~110 DEG C, more preferably 105
~108 DEG C；The time of the drying is preferably 11~13h, more preferably 12h；The granularity of the grinding is preferably 100~200
Mesh, more preferably 130~180 mesh；Specifically, in an embodiment of the present invention, can specifically used medicinal material grinder ground.
In the present invention, sawdust is the waste material generated when timber is processed, and the present invention is not special to the source of the sawdust
Restriction, directly can collect to obtain in wood-working factory.The present invention preferably pre-processes wood raw material, described pretreated
Method is in addition to grind size, other are consistent with the preprocess method of Enteromorpha, and details are not described herein；The grind size of the sawdust is excellent
It is selected as 40~60 mesh, more preferably 45~55 mesh.
In the present invention, the residual oil is crude oil through being evaporated under reduced pressure resulting residual oil, is gone out from atmospheric and vacuum distillation unit bottom
The heavy constituent come is C12Above macromolecule hydrocarbon mixture, wherein being reduced crude from atmospheric unit, from subtracting
Pressure device is decompression residuum.In the present invention, the residual oil is preferably the decompressed wax oil that boiling point boiling range is 350~500 DEG C.
In the present invention, carrying out the biomass of co carbonization reaction and the mass ratio of residual oil is preferably 0~0.5:1, more
Preferably 0.1~0.3:1.The present invention is mixed with biomass again after residual oil is preferably heated to flowing；In the present invention, described to add
The temperature of heat is preferably 40~60 DEG C, and more preferably 45~55 DEG C.
In the present invention, the temperature of the co carbonization reaction is preferably 400~500 DEG C, and more preferably 430~480 DEG C, most
Preferably 450 DEG C；The time of the co carbonization reaction is preferably 3~5h, more preferably 3.5~4.5h, most preferably 4h.
It in an embodiment of the present invention, can specifically used co carbonization reaction kettle progress co carbonization reaction.In portion of the invention
Divide in specific embodiment, reaction kettle can be preheated first, then co carbonization reaction kettle is put into heating furnace, then is warming up to altogether
Pyrogenetic reaction temperature, in co carbonization reaction process, co carbonization reaction kettle is connected with liquid receiver, for receiving biomass and slag
The crude oil that the raw co carbonization reaction of fry dried food ingredients generates, residual residue is required for the present invention to co carbonization in reaction kettle after the reaction was completed
Coking altogether.In the present invention, the temperature of the preheating is preferably 100~110 DEG C, and more preferably 105~108 DEG C；It is warming up to institute
The heating rate for stating preheating temperature is preferably 5~10 DEG C/min, more preferably 7~8 DEG C/min；It is warming up to the co carbonization reaction
The heating rate of temperature is preferably 30~70 DEG C/min, more preferably 40~60 DEG C/min, the co carbonization reaction time of the invention
It calculates since when being warming up to co carbonization reaction temperature.
Co carbonization reaction unit of the invention preferably includes: temperature controller, heating furnace, co carbonization reaction kettle, liquid receiver
With ice-water bath container；The temperature controller is connected with co carbonization reaction kettle, for monitoring co carbonization reaction kettle internal temperature；It is described total
Pyrogenetic reaction kettle top portion is provided with inert gas air inlet and delivery line, and the delivery line is connected with liquid receiver；The liquid
Body receiver, which is placed in ice-water bath container, carries out ice-water bath, the crude oil generated for receiving co carbonization reaction；The liquid connects
It receives and is provided with escape pipe at the top of device；The heating furnace is not connected with other devices, after co carbonization reaction kettle is warming up to preheating temperature,
It is put into heating furnace and is warming up to co carbonization reaction temperature and is reacted.
After the co carbonization reaction, present invention preferably uses cold water to be cooled to room temperature co carbonization reaction kettle, the cold water
Temperature be preferably 3~10 DEG C, more preferably 4~6 DEG C；
After the cooling, the present invention is dry after preferably crushing the product being collected into, and obtains total coking.In the present invention
In, the granularity of the crushing is preferably 70~90 mesh, more preferably 80 mesh；The temperature of the drying is preferably 100~110 DEG C,
The time of the drying is preferably 4~6h, more preferably 5h.
After obtaining total coking, the present invention successively carries out hydrophily pretreatment to the coking altogether and except ash content pre-processes, obtains
To pretreated coking altogether.In the present invention, the hydrophily pretreatment is preferably acid solution with hydrophilic agent；The acidity
Solution is preferably the mixture of one or more of sulfuric acid solution, nitric acid solution and phosphoric acid solution；The matter of the acid solution
Measuring concentration is preferably 40~60%, and more preferably 45~55%.
In the present invention, hydrophily pretreatment is preferred specifically: after total coking and acid solution are mixed successively into
Row ultrasound and stirring, obtain hydrophily and are total to coking.In the present invention, the ratio between the quality and the volume of acid solution of the coking altogether
Preferably 1g:8~15ml, more preferably 1g:10~12ml；The frequency of the ultrasound is preferably 300~500W, more preferably
350~450W；The time of the ultrasound is preferably 20~60min, more preferably 30~40min；The revolving speed of the stirring is preferred
For 300~500r/min, more preferably 350~450r/min；The time of the stirring is preferably 10~15h, and more preferably 11
~12h；The stirring is preferably magnetic agitation.
After the stirring, the material after stirring is preferably filtered, washed and dried by the present invention, is obtained hydrophily and is refined altogether
It is burnt.In the present invention, it is preferable to use deionized water washings for the washing, until washing to washing water is neutral；The drying
Temperature is preferably 100~110 DEG C, and more preferably 105~108 DEG C；The time of the drying is preferably 10~15h, more preferably
11~13h, most preferably 12h.
The present invention makes total coking surface combine hydrophilic radical by hydrophily pretreatment, so as to improve the hydrophilic of total coking
Property, in order to subsequent activation processing.
After the hydrophily pretreatment, the present invention is total to coking to obtained hydrophily and pre-process except ash content.In this hair
It is described except ash content pretreatment with deashing agent is preferably alkaline solution in bright；The alkaline solution is preferably that alkaline hydrated oxide is molten
Liquid, more preferably potassium hydroxide solution and/or sodium hydroxide solution；The concentration of the alkaline solution is preferably 1~2mol/L, more
Preferably 1.3~1.5mol/L.
In the present invention, it is described except ash content pretreatment is preferred specifically: after hydrophily is total to coking and alkaline solution mixing
It is heated to reflux, obtains pretreated coking altogether.In the present invention, the temperature being heated to reflux is preferably 100~140
DEG C, more preferably 110~130 DEG C；The time being heated to reflux is preferably 5~10h, more preferably 6~8h；The hydrophily
The quality of coking and the volume ratio of alkaline solution are preferably 1g:8~15ml altogether, more preferably 1g:10~12ml.
It is described be heated to reflux after, the reaction material liquid being heated to reflux preferably is filtered, washed and dried by the present invention,
Obtain pretreated coking altogether.In the present invention, the method being filtered, washed and dried and the pretreated mistake of hydrophily
Filter, washing are consistent with drying means, and details are not described herein.
The present invention improves the specific surface of finally obtained active carbon by removing the ash content in coking altogether except ash content pretreatment
And Kong Rong, to improve the adsorption capacity of active carbon.
After obtaining pretreated coking altogether, the present invention, will be described pretreated total under the conditions of inert gas shielding
Coking roasting, obtains biology base Carbon Materials.In the present invention, the inert gas is preferably He, Ar or N2, more preferably N2；Institute
The temperature for stating roasting is preferably 500~510 DEG C, and more preferably 505~508 DEG C；The time of the roasting is preferably 1~2h, more
Preferably 1.3~1.8h；Present invention preferably uses Muffle furnaces to be roasted.
After obtaining biology base carbon material, the present invention is under the conditions of inert gas shielding, by the biology base carbon material and work
Agent carries out priming reaction, obtains biomass-residual oil and is total to coking active carbon.In the present invention, the activator is preferably hydrogen-oxygen
The mixture of one or more of compound and bicarbonate；The hydroxide is preferably potassium hydroxide and/or sodium hydroxide；
The bicarbonate is preferably saleratus and/or sodium bicarbonate；The mass ratio of the activator and biology base carbon material is preferred
For 2~5:1, more preferably 3~4:1；The present invention is mixed with biology base carbon material again after preferably grinding activator；The grinding
Granularity be preferably 110~150 mesh, more preferably 120~130 mesh.In the present invention, the type and roasting of the inert gas
Inert gas type in the process is consistent, and details are not described herein.
In the present invention, the temperature of the priming reaction is preferably 800~805 DEG C, and more preferably 801~803 DEG C；Heating
Heating rate to the priming reaction temperature is preferably 8~15 DEG C/min, more preferably 10~12 DEG C/min；The activation is anti-
The time answered is preferably 1~2h, more preferably 1.3~1.5h；The priming reaction time is since when being warming up to required temperature
It calculates, the present invention preferably carries out priming reaction under constant temperature conditions.
After the priming reaction, the present invention uses hydrochloric acid and activation after preferably cooling to activation reaction product with the furnace room temperature
It is stirred after reaction product mixing, to remove wherein unreacted activator.In the present invention, the concentration of the hydrochloric acid is preferred
For 1~2mol/L, more preferably 1.3~1.5mol/L；The volume and activator mass ratio of the hydrochloric acid are preferably 10~20ml:
1g, more preferably 13~15ml:1g；The revolving speed of the stirring is preferably 300~500r/min, more preferably 350~450r/
min；The time of the stirring is preferably 10~30min, more preferably 15~20min.
After removing unreacted activator, obtained activation reaction product is successively washed and is done by the present invention
It is dry, it obtains biomass-residual oil and is total to coking active carbon.In the present invention, the washing is preferably washed；The detergent of the washing
Preferably deionized water；The pH of the washing preferably washing to washing water is 6.8~7.2；The temperature of the drying is preferably
100~110 DEG C, more preferably 105~108 DEG C；The time of the drying is preferably 4~6h, more preferably 4.5~5.5h, most
Preferably 5h.
In the present invention, it is preferably transition metal support type biomass-residual oil that the biomass-residual oil, which is total to coking active carbon,
Coking active carbon altogether.
In the present invention, the metal load type biomass-residual oil is total to coking active carbon preferably by including the following steps
Preparation method obtains:
Biomass-residual oil is total to after coking active carbon impregnates in transition metal salt solution to dry work after being impregnated
Property carbon；
By the activated carbon roasting after the dipping, transition metal load type active carbon is obtained.
Biomass-residual oil is total to drying after coking active carbon impregnates in transition metal salt solution by the present invention, is impregnated
Activated carbon afterwards.In the present invention, the transition metal is preferably the mixing of one or more of nickel, silver, zinc, cobalt and cerium
Object；The transition metal salt solution is preferably transition metal nitrate solution, transition metal HCI solution and Transition Metal Sulfur
The mixture of one or more of acid salt solution；The concentration of the transition metal salt solution is preferably 0.5~0.7mol/L, more
Preferably 0.6mol/L.
In the present invention, the dipping is preferably double-steeping, comprising the following steps: it is living that biomass-residual oil is total to coking
Property charcoal carried out in transition metal salt solution after the first dipping it is first dry, by the first active carbon after dry in transition metal salt
The second dipping, the active carbon after being impregnated after dry are carried out in solution.In the present invention, first dipping and the second dipping
In the concentration of transition metal salt solution be independently 0.5~0.7mol/L, more preferably 0.6mol/L；It is described first dipping and
Independent preferably 45~50 DEG C, more preferably 46~48 DEG C of the temperature of second dipping；First dipping and the second dipping
Time independent preferably 7~9h, more preferably 8h；Described first dry and the second dry temperature independent preferably 110
~130 DEG C, more preferably 115~125 DEG C, most preferably 120 DEG C；Described first dry and the second drying time is independent excellent
It is selected as 1~3h, more preferably 2h；Biomass-the residual oil is total to the quality of coking active carbon and the volume of transition metal salt solution
Than being preferably 1g:8~15ml, more preferably 1g:10~12ml.
The present invention enables transition metal ions to be evenly distributed in activated carbon surface by double-steeping, in order to rear
Continuous roasting process can obtain the active carbon of metal ion Load Balanced.
After the dipping, the present invention roasts the activated carbon after obtained dipping, obtains transition metal load type active carbon.
In the present invention, the temperature of the roasting is preferably 500~510 DEG C, more preferably 503~508 DEG C, most preferably 505 DEG C；Institute
The time for stating roasting is preferably 1.5~3.5h, more preferably 1.8~3h, most preferably 2h；It is described to be warming up to the maturing temperature
Heating rate be preferably 8~15 DEG C/min, more preferably 10~12 DEG C/min；The calcining time is warming up to required temperature certainly
When start to calculate, the present invention preferably roasts under constant temperature conditions.
Biomass-residual oil is total to coking activated carbon application and adsorbs desulfurization in crude oil by the present invention.The present invention is preferably by active carbon
Absorption desulfurization is carried out after directly mixing with crude oil.In the present invention, the quality of absorption the sweetening process Crude Oil and active carbon
Than being preferably 1:15~25, more preferably 1:20；The temperature of the absorption is preferably 40~50 DEG C, and more preferably 45 DEG C；It is described
The time of absorption is preferably 2~4h, more preferably 3h.
The present invention is total to mercaptan and thioether sulfides in coking activated carbon adsorption crude oil using biomass-residual oil, and
It can be difficult to the condensed ring thiophene class compound removed by the methods of hydrodesulfurization in adsorbing and removing crude oil, to reach depth suction
The effect of attached desulfurization.
Being total to carrying transition metal on coking active carbon in biomass-residual oil can be improved the adsorption capacity of active carbon, make to live
Property charcoal have physical absorption ability, but also with chemical adsorption capacity, further increase active carbon in crude oil absorption desulfurization
Desulfurization degree.
Below with reference to embodiment to biomass-residual oil provided by the invention be total to the preparation method and application of coking active carbon into
Row detailed description, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
The sawdust for collecting Qingdao periphery wood-working factory, cleans sawdust three times with clear water, in ventilation natural air drying, by wind
Sawdust after dry, which is put, dries 12h at 105 DEG C in an oven, grinds the sawdust of drying with medicinal material grinder, chooses partial size mesh
Sawdust of the number in 40~60 mesh；
Residual oil 300g is placed in a beaker, flow regime is heated to, 30g sawdust is added and is transferred to co carbonization after mixing
Reaction kettle is preheated to 100 DEG C (heating rate is 8 DEG C/min), after rising to preheating temperature, co carbonization reaction kettle is turned by reaction kettle
It moves in heating furnace, is warming up to 450 degrees Celsius (heating rate is 30 DEG C/min), N2In 450 DEG C of isothermal reaction 4h under atmosphere；Instead
Co carbonization reaction kettle is taken out after the completion of answering, cold water rapid cooling to room temperature from heating furnace, product is smashed it through into 80 meshes,
The dry 5h in 105 DEG C of drying boxes, obtains total coking；
The sulfuric acid that total coking and mass concentration are 50% is mixed with the ratio of 1g:10ml, magnetic force after ultrasonic vibration 30min
12h is stirred, is then filtered with Buchner funnel, 12h will be dried after Washing of Filter Cake to neutrality at 100 DEG C with deionized water, obtained
Hydrophilic coking altogether；
The NaOH solution of total coking and 1mol/L after hydrophilic treated is mixed with the ratio of 1g:10ml, mixture is existed
Flow back 5h under the conditions of 100 DEG C, and filtered on buchner funnel is used after the completion of reflux, using deionized water by Washing of Filter Cake to neutrality,
Dry 12h at 100 DEG C, obtains pretreated coking altogether；
In N2Under protection, pretreated coking altogether is roasted into 1h, the biology collected after natural cooling at 500 DEG C
Base Carbon Materials；
By KOH grind into powder, KOH and biology base Carbon Materials are put into mass ratio for the ratio of 3:1 after mixing
In porcelain boat, porcelain boat is put into high temperature resistance furnace, in N2Under protection, 800 DEG C of constant temperature activation 1h (heating rate is 10 DEG C/min),
It takes out after its natural cooling, is reacted with the dilute hydrochloric acid of 1mol/L with activation reaction product, remove unreacted activator, react
It filters and is rinsed to neutrality after the completion, filter cake is obtained into biomass-residual oil after dry 1h at 100 DEG C and is total to coking active carbon；
The specific surface area of coking active carbon is total to gained biomass-residual oil and total pore volume detects, active carbon ratio can be obtained
Surface area is 2133.3m2/ g, total hole volume 1.38cm3/g；
Gained active carbon is observed using scanning electron microscope, observed result is as shown in Figure 1, Fig. 1 (a) is amplification
The scanning electron microscope diagram piece that 4500 multiples are 4500 times, Fig. 1 (b) is the scanning electron microscope that amplification factor is 5000 times
Picture；According to Fig. 1 as can be seen that having pore structure abundant inside obtained activated carbon, and pore structure can extend to activity
Inside charcoal particle.
Embodiment 2
The Enteromorpha that Qingdao Golden Beach is salvaged is cleaned three times with clear water, dries 12h at 105 DEG C, it will with medicinal material grinder
The sawdust of drying is ground, and chooses partial size mesh number in the Enteromorpha of 100~200 mesh；
Decompressed wax oil 300g is placed in a beaker, flow regime is heated to, 120g Enteromorpha is added and is transferred to after mixing
Reaction kettle is preheated to 110 DEG C (heating rate is 10 DEG C/min), after rising to preheating temperature, by co carbonization by co carbonization reaction kettle
Reaction kettle is transferred in heating furnace, is warming up to 500 DEG C (heating rate is 50 DEG C/min), N2In 450 DEG C of isothermal reactions under atmosphere
4h；Co carbonization reaction kettle is taken out from heating furnace after the reaction was completed, product is smashed it through 80 by cold water rapid cooling to room temperature
Mesh, the dry 5h in 105 DEG C of drying boxes, obtains total coking；
The nitric acid that total coking and mass concentration are 50% is mixed with the ratio of 1g:10ml, magnetic force after ultrasonic vibration 20min
11h is stirred, is then filtered with Buchner funnel, 12h will be dried after Washing of Filter Cake to neutrality at 105 DEG C with deionized water, obtained
Hydrophilic coking altogether；
The KOH solution of total coking and 1mol/L after hydrophilic treated is mixed with the ratio of 1g:10ml, mixture is existed
Flow back 6h under the conditions of 140 DEG C, and filtered on buchner funnel is used after the completion of reflux, using deionized water by Washing of Filter Cake to neutrality,
Dry 12h at 100 DEG C, obtains pretreated coking altogether；
In N2Under protection, pretreated coking altogether is roasted into 1h at 500 DEG C, roasting process uses N2Protection, it is naturally cold
But the biology base Carbon Materials collected afterwards；
By KOH grind into powder, KOH and biology base Carbon Materials are put into mass ratio for the ratio of 4:1 after mixing
In porcelain boat, porcelain boat is put into high temperature resistance furnace, in N2Under protection, 800 DEG C of constant temperature activation 1h (heating rate is 10 DEG C/min),
It takes out after its natural cooling, is reacted with the dilute hydrochloric acid of 2mol/L with activation reaction product, remove unreacted activator, react
It filters and is rinsed to neutrality after the completion, filter cake is obtained into biomass-residual oil after dry 1h at 105 DEG C and is total to coking active carbon；
The specific surface area of coking active carbon is total to gained biomass-residual oil and total pore volume detects, active carbon ratio can be obtained
Surface area is 2351.6m2/ g and total hole volume 1.47cm3/g；
Gained active carbon is observed using scanning electron microscope, observed result is as shown in Fig. 2, Fig. 2 (a) is amplification
The electron microscope picture that multiple is 3000 times, Fig. 2 (b) is the electron microscope picture that amplification factor is 5000 times；According to fig. 2
As can be seen that obtained activated carbon internal pore structure is abundant similar with embodiment 1, the hole on different samples cannot penetrate through whole
The inside of a particle, and be distributed across on each different layers of active carbon particle.
Embodiment 3
Preparing Enteromorpha that partial size mesh number is 100~200 mesh and partial size mesh number respectively according to the method for Examples 1 to 2 is 40
The sawdust of~60 mesh；
Decompressed wax oil 300g is placed in a beaker, flow regime is heated to, 40g Enteromorpha and 50g sawdust is added, is uniformly mixed
After be transferred to co carbonization reaction kettle, reaction kettle is preheated to 105 DEG C (heating rates be 5 DEG C/min), will after rising to preheating temperature
Co carbonization reaction kettle is transferred in heating furnace, is warming up to 480 DEG C (heating rate is 70 DEG C/min), N2In 480 DEG C of perseverances under atmosphere
Temperature reaction 6h；Co carbonization reaction kettle is taken out from heating furnace after the reaction was completed, cold water rapid cooling to room temperature crushes product
80 meshes are crossed afterwards, and the dry 4h in 110 DEG C of drying boxes obtains total coking；
The phosphoric acid that total coking and mass concentration are 40% is mixed with the ratio of 1g:10ml, magnetic force after ultrasonic vibration 25min
12h is stirred, is then filtered with Buchner funnel, 12h will be dried after Washing of Filter Cake to neutrality at 110 DEG C with deionized water, obtained
Hydrophilic coking altogether；
The KOH solution of total coking and 2mol/L after hydrophilic treated is mixed with the ratio of 1g:10ml, mixture is existed
Flow back 8h under the conditions of 120 DEG C, and filtered on buchner funnel is used after the completion of reflux, using deionized water by Washing of Filter Cake to neutrality,
Dry 12h at 100 DEG C, obtains pretreated coking altogether；
In N2Under protection, pretreated coking altogether is roasted into 1h at 505 DEG C, roasting process uses N2Protection, it is naturally cold
But the biology base Carbon Materials collected afterwards；
By NaOH grind into powder, NaOH and biology base Carbon Materials are put with mass ratio for the ratio of 3:1 after mixing
Enter in porcelain boat, porcelain boat is put into high temperature resistance furnace, in N2Under protection, 803 DEG C of constant temperature activation 1h (heating rate is 10 DEG C/
Min), take out after its natural cooling, reacted with the dilute hydrochloric acid of 1.5mol/L with activation reaction product, remove unreacted activation
Agent filters rinse to neutrality after the reaction was completed, and filter cake is obtained after dry 1.5h to biomass-residual oil at 100 DEG C and is total to coking work
Property charcoal；
The specific surface area of coking active carbon is total to gained biomass-residual oil and total pore volume detects, active carbon ratio can be obtained
Surface area is 2401.6m2/ g and total hole volume 1.52cm3/g；
Gained active carbon is observed using scanning electron microscope, observed result embodiment 1 is similar.
Embodiment 4
Decompressed wax oil 300g is placed in a beaker, co carbonization reaction kettle is transferred to after being heated to flow regime, by reaction kettle
110 DEG C (heating rate is 8 DEG C/min) are preheated to, after rising to preheating temperature, co carbonization reaction kettle is transferred in heating furnace, is risen
Temperature is to 450 DEG C (heating rate be 60 DEG C/min), N2In 450 DEG C of isothermal reaction 4h under atmosphere；It is after the reaction was completed that co carbonization is anti-
Kettle is answered to take out from heating furnace, product is smashed it through 80 meshes by cold water rapid cooling to room temperature, is done in 110 DEG C of drying boxes
Dry 5h obtains residual oil coke；
The sulfuric acid that residual oil coke and mass concentration are 45% is mixed with the ratio of 1g:12ml, magnetic force after ultrasonic vibration 30min
12h is stirred, is then filtered with Buchner funnel, 12h will be dried after Washing of Filter Cake to neutrality at 110 DEG C with deionized water, obtained
Hydrophilic coking altogether；
The KOH solution of total coking and 1.5mol/L after hydrophilic treated is mixed with the ratio of 1g:10ml, mixture is existed
Flow back 5h under the conditions of 130 DEG C, and filtered on buchner funnel is used after the completion of reflux, using deionized water by Washing of Filter Cake to neutrality,
Dry 12h at 100 DEG C, obtains pretreated coking altogether；
In N2Under protection, pretreated coking altogether is roasted into 1h at 500 DEG C, roasting process is protected using N2, natural
The biology base Carbon Materials collected after cooling；
By NaOH grind into powder, by NaOH and biology base Carbon Materials with mass ratio for 3.5:1 ratio after mixing
It is put into porcelain boat, porcelain boat is put into high temperature resistance furnace, in N2Under protection, 805 DEG C of constant temperature activation 1h (heating rate is 10 DEG C/
Min), take out after its natural cooling, reacted with the dilute hydrochloric acid of 1.2mol/L with activation reaction product, remove unreacted activation
Agent filters rinse to neutrality after the reaction was completed, and filter cake is obtained residual oil coke active carbon after dry 1h at 100 DEG C；
The specific surface area and total pore volume of gained residual oil coke active carbon are detected, can obtain active carbon specific surface area is
2301.6m2/ g and total hole volume 1.36cm3/g；
Gained active carbon is observed using scanning electron microscope, observed result embodiment 1 is similar.
Embodiment 5
Using tube oven method, crude oil suction is carried out to the active carbon that Claims 1 to 4 obtains referring to the standard of GB/T387-90
Attached desulfurization performance test, the crude oil used is Saudi Arabia's middle matter crude oil, and the specific method is as follows:
By Examples 1 to 4 prepare biomass-residual oil be total to coking active carbon respectively with Saudi Arabia's middle matter crude oil according to
The ratio of 1g:20g mixes in round-bottomed flask, after 55 DEG C of temperature constant magnetic stirring 3h, with strainer by after desulfurization crude oil and activity
The separation of charcoal solid is put into the measurement that preparation in small beaker carries out sulfur content；
The measurement of sulfur content uses tube oven method, and the specific method is as follows:
It weighs certain mass crude oil to be covered behind porcelain boat bottom with quartz sand, porcelain boat is put into quartz ampoule, is passed through immediately
Air stream, the flow velocity of air are 500mL/min, then roast 45min under conditions of temperature is 920 DEG C, the product of burning by
Mixed solution absorbs, and mixed solution is by H2SO4 (mass concentration 98%), H2O2 (mass concentration 20%) and H2O according to body
Product titrates mixed solution with NaOH standard solution after having reacted, and calculate sulphur and contain than being that the ratio of 7:5:150 is made into
Amount, calculation formula are as follows:
Wherein, WSFor the sulfur content in sample, %；MSFor the half of the molal weight of sulphur, 16g/mol；C (NaOH) is mark
Surely the actual concentrations used, mol/L；V2For the volume of the NaOH of consumption, mL；V0 is the volume of the NaOH of blank test consumption,
ML, m2For the quality for weighing oil product, g.
The sulfur content before adsorbing in crude oil and after absorption is measured respectively, calculates desulfurization degree, by the results are shown in Table 1；
Biomass-residual oil obtained by 1 Examples 1 to 4 of table is total to the crude oil absorption desulfurization performance test result of coking active carbon
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Desulfurization degree/% | 22.6 | 20.4 | 21.3 | 19.6 |
According to table 1 as can be seen that biomass-residual oil is total to coking activated carbon application in crude oil absorption desulfurization, can obtain
To preferable desulfurization effect, and sulfur method is simple, and biomass-residual oil is total to application of the coking active carbon in crude oil absorption desulfurization
The development and progress of desulfurizing oil technology must be will further facilitate.
Embodiment 6
The Enteromorpha that partial size mesh number is 100~200 mesh is prepared according to the method for embodiment 2；
Decompressed wax oil 300g is placed in a beaker, flow regime is heated to, 30g Enteromorpha is added and is transferred to after mixing altogether
Reaction kettle is preheated to 110 DEG C (heating rate is 10 DEG C/min) by pyrogenetic reaction kettle, after rising to preheating temperature, co carbonization is anti-
It answers kettle to be transferred in heating furnace, is warming up to 450 DEG C (heating rate is 50 DEG C/min), N2In 450 DEG C of isothermal reaction 4h under atmosphere；
Co carbonization reaction kettle is taken out after the reaction was completed, cold water rapid cooling to room temperature from heating furnace, product is smashed it through into 80 mesh
Sieve, the dry 5h in 105 DEG C of drying boxes, obtains total coking；
The nitric acid that total coking and mass concentration are 50% is mixed with the ratio of 1g:10ml, magnetic force after ultrasonic vibration 20min
11h is stirred, is then filtered with Buchner funnel, 12h will be dried after Washing of Filter Cake to neutrality at 105 DEG C with deionized water, obtained
Hydrophilic coking altogether；
The KOH solution of total coking and 1mol/L after hydrophilic treated is mixed with the ratio of 1g:10ml, mixture is existed
Flow back 6h under the conditions of 140 DEG C, and filtered on buchner funnel is used after the completion of reflux, using deionized water by Washing of Filter Cake to neutrality,
Dry 12h at 100 DEG C, obtains pretreated coking altogether；
In N2Under protection, pretreated coking altogether is roasted into 1h at 500 DEG C, roasting process uses N2Protection, it is naturally cold
But the biology base Carbon Materials collected afterwards；
By KOH grind into powder, KOH and biology base Carbon Materials are put into mass ratio for the ratio of 3:1 after mixing
In porcelain boat, porcelain boat is put into high temperature resistance furnace, in N2Under protection, 800 DEG C of constant temperature activation 1h (heating rate is 10 DEG C/min),
It takes out after its natural cooling, is reacted with the dilute hydrochloric acid of 2mol/L with activation reaction product, remove unreacted activator, react
It filters and is rinsed to neutrality after the completion, filter cake is obtained into biomass-residual oil after dry 1h at 110 DEG C and is total to coking active carbon；
By the Zn (NO that gained biomass-residual oil is total to coking active carbon and concentration is 0.6mol/L3)2Solution mixes (mixing ratio
Example 1g:10ml), 8h is impregnated under the conditions of 45 DEG C, filtering and the dry 1h under the conditions of 120 DEG C after dipping, by the activity after drying
Charcoal impregnates 8h under the same conditions again, dries 1h after filtering under the conditions of 120 DEG C, the sample after drying is put into high temperature resistance
In furnace, in N2500 DEG C of constant temperature 2h in atmosphere, take out after its natural cooling, obtain the active carbon of load zinc ion；
The specific surface area of coking active carbon is total to gained metal load type biomass-residual oil and total pore volume detects, it can
Obtaining active carbon specific surface area is 2334.0m2/ g and total hole volume 1.5cm3/g；
Gained active carbon is observed using scanning electron microscope, observed result is as shown in figure 4, Fig. 4 (a) is amplification
The electron microscope picture that multiple is 1000 times, Fig. 4 (b) is the electron microscope picture that amplification factor is 5000 times；According to Fig. 4
As can be seen that metallic is uniformly dispersed on the activated carbon, without agglomeration.
The active carbon of gained load zinc ion is subjected to crude oil absorption desulfurization performance test, can obtain desulfurization degree is 32.4%.
Embodiment 7
Coking active carbon is total to according to method preparation biomass-residual oil in embodiment 6；
By the Ni (NO that gained biomass-residual oil is total to coking active carbon and concentration is 0.6mol/L3)2Solution mixes (mixing ratio
Example 1g:10ml), 7h is impregnated under the conditions of 50 DEG C, filtering and the dry 1h under the conditions of 110 DEG C after dipping, by the activity after drying
Charcoal impregnates 7.5h under the same conditions again, dries 1h after filtering under the conditions of 110 DEG C, the sample after drying is put into high-temperature electric
It hinders in furnace, in N2510 DEG C of constant temperature calcining 1.5h in atmosphere, take out after its natural cooling, obtain the active carbon of load nickel ion；
The active carbon of gained load nickel ion is subjected to crude oil absorption desulfurization performance test, can obtain desulfurization degree is 32.3%.
Gained active carbon is observed using scanning electron microscope, observed result and embodiment 7 are similar.
As seen from the above embodiment, the present invention prepares active carbon using biomass and residual oil as raw material, utilizes biological close-burning structure
The characteristics of loose, mechanical strength is low and petroleum coke compact structure, high mechanical strength has obtained high-specific surface area, high total pore volume
The activated carbon application can be obtained preferable desulfurization effect in crude oil absorption desulfurization by active carbon；Active carbon is subjected to metal
It can be improved the absorption desulfurization performance in crude oil of active carbon after loaded modified；And in the present invention active carbon raw material sources it is wide
It is general, it is at low cost, it further reduced the cost of crude oil absorption desulfurization.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (8)
1. a kind of biomass-residual oil is total to application of the coking active carbon in crude oil absorption desulfurization, which is characterized in that the biology
Matter-residual oil is total to coking active carbon and is obtained by the preparation method included the following steps:
Under inert gas protection, biomass and residual oil are subjected to co carbonization reaction, obtain total coking；The biomass and residual oil
Mass ratio be greater than 0 be less than or equal to 0.5；The temperature of the co carbonization reaction is 400~500 DEG C；The co carbonization reaction
Time is 3~5h；
Hydrophily pretreatment is successively carried out to the coking altogether and except ash content pre-processes, obtains pretreated coking altogether；It is described
Except ash content pretreatment is alkaline solution with deashing agent；
Under inert gas protection, by the pretreated coking roasting altogether, biology base Carbon Materials are obtained；
Under inert gas protection, the biology base Carbon Materials and activator are subjected to priming reaction, it is total obtains biomass-residual oil
Coking active carbon.
2. application according to claim 1, which is characterized in that the biomass is sawdust and/or Enteromorpha.
3. application according to claim 1, which is characterized in that the temperature of the roasting is 500~510 DEG C；The roasting
Time be 1~2h.
4. application according to claim 1, which is characterized in that the activator is one in hydroxide and bicarbonate
Kind or several mixtures；The mass ratio of the activator and biology base Carbon Materials is 2~5:1.
5. application according to claim 1, which is characterized in that the temperature of the priming reaction is 800~805 DEG C；It is described
The time of priming reaction is 1~2h.
6. application according to claim 1, which is characterized in that it is transition gold that the biomass-residual oil, which is total to coking active carbon,
Belong to support type biomass-residual oil and is total to coking active carbon.
7. application according to claim 6, which is characterized in that the transition metal support type biomass-residual oil is total to coking
Active carbon is obtained by the preparation method included the following steps:
Biomass-residual oil is total to after coking active carbon impregnates in transition metal salt solution to dry active carbon after being impregnated；
By the active carbon roasting after the dipping, obtains transition metal load type biomass-residual oil and be total to coking active carbon.
8. application according to claim 7, which is characterized in that the dipping is double-steeping, comprising the following steps:
Biomass-residual oil is total to coking active carbon and is carried out in transition metal salt solution after the first dipping first dry, will be dried
Active carbon afterwards carries out the second dipping, the active carbon after being impregnated after the second drying in transition metal salt solution；Described
The concentration of one dipping and the transition metal salt solution in the second dipping is independently 0.5~0.7mol/L.
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