CN108704672A - Ebullated bed wood tar adds the on-line regeneration method and apparatus of hydrogen decaying catalyst - Google Patents
Ebullated bed wood tar adds the on-line regeneration method and apparatus of hydrogen decaying catalyst Download PDFInfo
- Publication number
- CN108704672A CN108704672A CN201810551650.3A CN201810551650A CN108704672A CN 108704672 A CN108704672 A CN 108704672A CN 201810551650 A CN201810551650 A CN 201810551650A CN 108704672 A CN108704672 A CN 108704672A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- oil
- solvent
- eddy flow
- micro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
- B01J38/52—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids oxygen-containing
-
- C—CHEMISTRY; METALLURGY
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/14—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with moving solid particles
- C10G45/20—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with moving solid particles according to the "fluidised-bed" technique
-
- C—CHEMISTRY; METALLURGY
- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- 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
- C10G2300/70—Catalyst aspects
- C10G2300/703—Activation
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
This disclosure relates to ebullated bed wood tar adds the on-line regeneration method and apparatus of hydrogen decaying catalyst, a kind of on-line regeneration method that ebullated bed wood tar adds hydrogen decaying catalyst is provided, this approach includes the following steps：(A) it is arranged outside catalyst and strains oil；(B) catalyst, lean solvent mixing；(C) micro- eddy flow extraction is washed；(D) solvent is reduced；(E) solvent reclamation；And (F) metal reduction.Additionally provide the on-line regeneration facility that a kind of ebullated bed wood tar adds hydrogen decaying catalyst.
Description
Technical field
The disclosure belongs to biomass energy and oil product manufacture field, be related to it is a kind of to ebullated bed wood tar add hydrogen inactivation catalysis
The on-line regeneration method and apparatus of agent.Specifically, present disclose provides a kind of ebullated bed wood tar to add hydrogen decaying catalyst
On-line regeneration method and apparatus.
Background technology
In face of the dual-pressure of the energy and environment, the urgent mesh that clean regenerative resource has become the world today is developed
Mark.Biomass energy has that amount is big, distribution is wide, easily obtain, easy advantages such as storage, environmental protection, thus biomass energy transformation technology is just
As the hot spot of various countries' research.
From stalk, timber used during fast thermal cracking in, wood tar product can be obtained；By adding hydrogen that can obtain it
The fuel oil of high-quality.Since wood tar is easy to be condensed coking, catalyst life is short, preferably uses fluidized bed reactor technology in fact
Apply hydrogenation deoxidation.Boiling bed hydrogenation technology efficiently solve fixed bed reactors air speed is low, system pressure drop is big, easy coking, device
The problems such as cycle of operation is short.
During ebullated bed wood tar hydrogenation deoxidation, by fluidized bed reactor outer a large amount of decaying catalysts arranged online
A large amount of petroleum hydrocarbons are adsorbed with, if being unable to get rational processing, not only result in a large amount of wastes of oil, and
There are certain environmental risks；Meanwhile catalyst can not regenerate use so that wood tar adds hydrogen operating cost high.Cause
This can make device if outer row's catalyst regeneration process in ebullated bed wood tar hydrogenation technique can be solved the problems, such as
Outer waste discharge greatly reduces, improves the environment friendly of technique, reduces the operating cost of device, the industry for this technology admittedly
Change to promote and apply and be of great significance.
Currently, since there has been no ripe large-scale ebullated bed wood tar hydrogenation plants in the world, boiled for wood tar
The processing of bed hydroprocessing decaying catalyst is risen, also there has been no report for work.Therefore, industrialized boiling bed residual oil already also can be only referred to add
The processing mode of catalyst is arranged outside hydrogen production device, mainly based on calcination, landfill, not only processing cost is higher, for catalyst and
Oil is all greatly to waste, and can cause secondary pollution.
To realize that the reasonable efficient utilization for arranging decaying catalyst outside ebullated bed, many researchers have been carried out to oil-containing
Arrange the treatment research of catalyst.
Chinese patent application CN 102527448A disclose a kind of catalyst de-oiling method and device, described device include
De-oiling tank, gas-liquid separator, oil-gas pipeline, cyclic nitrogen compressor, nitrogen pipeline, oil gas water cooler, cyclic nitrogen heater and oil
Gas-nitrogen heat exchanger.The temperature for entering nitrogen in de-oiling device is increased by cyclic nitrogen heater, and heat is brought into de-oiling tank
In, so that the oil phase in de-oiling tank is gasified, and escape from de-oiling tank with nitrogen, into oil gas-nitrogen heat exchanger, the oil after heat exchange
Gas-nitrogen mixture enters oil gas water cooler, the oil gas condensation and and nitrogen separation, realize the separation of oil and catalyst.
But the heating means used in this application is oil phase vaporization, temperature need to reach 280-300 DEG C in de-oiling tank, and want constant temperature 4-
8 hours, energy consumption was very big；And the quick processing of catalyst is cannot achieve, is not suitable for for one day in entire temperature-rise period
The boiling bed hydrogenation technique arranged outside catalyst on-line continuous.Moreover, this application can only also realize the separation of catalyst and oil phase, nothing
Method realizes the regeneration technology of catalyst.
3541002 A of U.S. Patent application US disclose a kind of regeneration method of beaded catalyst, are particularly suitable for fluidizing
Bed and ebullated bed, this method take out catalyst by semi-continuous from reactor, with flushing oil with certain flow velocity to taking out
Catalyst rinsed upwards, make catalyst volume expansion be in fluidized state, isolate oil phase to obtain dry catalysis
Agent particle, dry catalyst are stored into the first renewing zone, the outer row catalysis for waiting the first renewing zone to be collected into general 7 days
When agent, start regenerative operation, realizes that the regeneration of catalyst, regenerated catalyst are semi-continuously returned in reactor and recycled.
This application includes two renewing zones, can be regenerated to dry catalyst.But this method can only realize it is semicontinuous, and
And it is not high to the separative efficiency of catalyst and oil, processing cannot the continuous and period it is longer.
Chinese patent application CN 103145306A disclose a kind of group technology of supercritical extraction processing oily sludge
And device, the group technology include level-one separation process and the second-order separation process, level-one separation process makes oil-containing catalyst exist
It is extracted under the conditions of boundary over zero, extraction phase enters the separation that the second-order separation process carries out crude oil and extractant.The technique can be same
When crude oil and extractant are recycled.But the technique needs fluid to reach the state of boundary over zero, i.e. temperature and pressure is super
Its critical point is crossed, supercritical fluid is become, the advantage of competence exertion its preferable permeability and stronger solvability is realized former
The efficient recycling of oil, reaches supercriticality and needs to expend more energy.Moreover, this application cannot achieve catalyst again
It is raw.
In conclusion the processing for arranging catalyst outside oil-containing at present often also cannot get ideal effect or de-oiling efficiency not
Height or the wasting of resources or complex process, or processing energy consumption and cost it is excessively high, some can also cause secondary pollution.Solve ebullated bed
Wood tar adds the regeneration issues that catalyst is arranged outside hydrogen, can not only eliminate harm of the outer row's catalyst to environment, moreover it is possible to cost is reduced,
Promote the development of ebullated bed wood tar hydrogenation technique.
Therefore, there is an urgent need in the art to develop effectively solve above-mentioned problems of the prior art, boiling is realized
Bed wood tar add the ebullated bed wood tar for the efficient process that catalyst is arranged outside hydrogen add the on-line regeneration method that catalyst is arranged outside hydrogen and
Device.
Invention content
The disclosure aims to solve the problem that the technical barrier arranged outside ebullated bed wood tar hydrogen addition technology in catalyst treatment, i.e.,：From boiling
It rises the outer catalyst arranged of interval in a wood tar hydrogenation reactor and contains a large amount of free oil and hole oil, it is difficult to realize catalyst
Particle and oil phase efficiently separate, and cause a large amount of oil product to waste, and can cause damages to environment；And existing treatment technology
Often in the presence of separation not exclusively, cannot operate continuously, the work period is long the problems such as；Meanwhile the catalyst granules obtained after separation
Due to being failed by oxidation in reaction process, the directly discarded significant wastage that can cause catalyst resource so that catalyst cost
It is high, hinder the development of ebullated bed wood tar hydrogen addition technology.
This disclosure relates to add row's catalyst outside hydrogen to revolve in ebullated bed wood tar using organic solvent in micro- eddy flow field
Strengthening extraction is flowed, concentrated by eddy flow after extraction and dries the organic solvent in removing de-oiling rear catalyst, You Jirong from returning charge
Agent carries out solvent reclamation by rectifying and returns to eddy flow extraction section, and de-oiling rear catalyst particle enters in rotary kiln, utilizes hydrogen pair
The inactivation metal aoxidized is restored, and realizes the regeneration of catalyst, is utilized again back to fluidized bed reactor, to overcome
Blank and defect existing in the prior art.
On the one hand, present disclose provides a kind of on-line regeneration method that ebullated bed wood tar adds hydrogen decaying catalyst, the party
Method includes the following steps：
(A) it is arranged outside catalyst and strains oil：The catalyst pulp being externally discharged implements gravity and strains oil, to isolate free oil；
(B) catalyst, lean solvent mixing：To in step (A) through sedimentation strain oil after gained catalyst granules and lean solvent
It is mixed, to form the homogeneous mixture of catalyst granules and lean solvent；
(C) micro- eddy flow extraction is washed:Micro- rotation is implemented to the homogeneous mixture of the catalyst granules of gained and lean solvent in step (B)
Stream is strengthened extraction and is washed so that and the oil phase that catalyst granules carries or sticks migrates into lean solvent, while being acted on using cyclonic separation,
Realize the separation of de-oiling rear catalyst particle and rich solvent；
(D) solvent is reduced：To the catalyst granules with organic solvent obtained after micro- eddy flow extraction is washed in step (C)
Implement eddy flow concentration and dried from returning charge, with the organic solvent of Removal of catalyst particle entrainment；
(E) solvent reclamation：Separation is implemented to the rich solvent obtained in step (C), obtains lean solvent and is followed with return to step (B)
Ring uses and oil phase is recycled；And
(F) metal restores：Catalyst granules after micro- eddy flow extracts elution oil, organic solvent decrement is restored,
So that the active metal reduction aoxidized on row's catalyst granules outside, has activity again.
In one preferred embodiment, in step (A), the catalyst pulp of the outer discharge is by ebullating bed reactor
The outer row of device interval, oil content are 50~70%, in mass；By straining oily process, also complete to the outer row's catalyst of interval
The storage cushioning effect of slurry.
In another preferred embodiment, in step (A), ebullated bed wood tar hydrogenation technique catalysis used
Agent is activated carbon supported type catalyst, and wherein active metallic element is iron, nickel, molybdenum or platinum.
In another preferred embodiment, in step (B), the lean solvent be methanol or ethyl alcohol, or with it is outer
The polar organic solvent that main oil phase component in the catalyst pulp of discharge mixes.
In another preferred embodiment, in step (B), the mixed proportion of catalyst granules and lean solvent is 1:
1~1:50, by quality ratio；It mixes by stirring, the stirring residence time is 1~30min；Control catalyst granules and lean solvent
Homogeneous mixture temperature be not higher than 100 DEG C.
In another preferred embodiment, the de-oiling catalyst granules that is obtained after the step (C) and step (D)
Oil content be less than 2%, dissolvent residual rate be less than 0.1%, in mass.
In another preferred embodiment, in step (E), using chemistry or physical separation means to step
(C) rich solvent obtained in implements separation.
It in another preferred embodiment, in step (F), is restored in hydrogen atmosphere using rotary kiln, also
Former temperature is 180~320 DEG C；Active metal through reduction is back to fluidized bed reactor reuse.
On the other hand, present disclose provides the on-line regeneration facilities that a kind of ebullated bed wood tar adds hydrogen decaying catalyst, should
Device includes：
Buffering strains oil tank, and the catalyst pulp for being externally discharged implements gravity and strains oil, to isolate free oil, and realizes
To the storage buffering of catalyst pulp；
The tank connected auger tank of oil is strained with buffering, for the catalyst granules of gained after oil is strained in sedimentation and poor molten
Agent is mixed, and to form the homogeneous mixture of catalyst granules and lean solvent, and regulates and controls the temperature and liquid-solid ratio of mixture；
Device is washed with tank connected micro- eddy flow extraction is stirred, is used to mix the catalyst granules of gained and the uniform of lean solvent
It closes the micro- eddy flow reinforcing extraction of object implementation to wash so that the oil phase that catalyst granules carries or sticks migrates into lean solvent, utilizes simultaneously
Cyclonic separation acts on, and realizes the separation of de-oiling rear catalyst particle and rich solvent；
Wash the eddy flow that device connect with micro- eddy flow extraction and be reduced device, and connect with eddy flow decrement device from returning charge drying machine, use
In implementing eddy flow concentration to the catalyst granules with organic solvent obtained after micro- eddy flow extraction is washed and from returning charge drying, with
The organic solvent of Removal of catalyst particle entrainment；
The rectifying column being connect with from returning charge drying machine obtains lean solvent to follow for implementing separation to obtained rich solvent
Ring uses and oil phase is recycled；And
The rotary kiln being connect with from returning charge drying machine, for after micro- eddy flow extracts elution oil, organic solvent decrement
Catalyst granules is restored so that the active metal reduction aoxidized on outer row's catalyst granules has activity again.
In one preferred embodiment, micro- eddy flow extraction washes device by more parallel connections, to meet the needs for the treatment of capacity；
Inlet velocity is not less than 8m/s；Import and oil-containing organic solvent outlet pressure drop≤0.15MPa；Top rich solvent exports solid content
≤5ppm；De-oiling catalyst particle exit flow in bottom is continuously adjustable, accounts for the 3~50% of inlet flow rate, in mass.
Advantageous effect：
The major advantage of methods and apparatus of the present invention is：
(1) degreasing process washes principle using micro- eddy flow extraction.The principle on the one hand by it is similar mix, interface update strengthen it is molten
The extraction process of soluble substance in catalyst is externally arranged in agent；On the other hand, it is realized using the high speed rotation of particle in micro- eddy flow field
The mechanical stripping process of insoluble material in outer row's catalyst.Also, micro- eddy flow extraction, which washes journey, to be operated continuously, and current
Extraction process is often intermittently operated, and extraction procedure is longer, and relies only on the similar principle that mixes, and extraction efficiency is not high.
(2) during micro- eddy flow extraction is washed, the centrifugal force that rotational flow field is formed completes point of the catalyst granules with organic solvent
It being completed at the same time extraction from a, equipment and washes journey and separation process so that it is short compared with traditional extraction technological process that micro- eddy flow extraction washes technique,
Equipment investment is few.
(3) it is used by the regeneration cycle of organic solvent, realizes and maintain larger extraction ratio during micro- eddy flow extraction is washed
(solvent:Solid > 40), meanwhile, ensure that carrying out micro- eddy flow extraction using the poor organic solvent after regeneration always washes, and ensure that extraction
There are the concentration gradient of bigger, the extracting extraction mode of more traditional fixed bed to possess higher extraction ratio, extraction efficiency higher in the process.
(4) use rotary kiln device, in a hydrogen atmosphere, to the catalyst granules after deoiling treatment into row metal also
Origin operation.Restoring operation process is carried out continuously, and catalyst granules and hydrogen come into full contact with, and reduction efficiency is high, flow is short, device connects
Continuous operation, operating condition are good, can be to avoid traditional batch fixed bed reductor operation cycle, the non-uniform situation of reduction.
Description of the drawings
Attached drawing is provided for further understanding of the disclosure, it simply forms the part of this specification with into one
Step explains the disclosure, does not constitute the limitation to the disclosure.
Fig. 1 is the technique that boiling wood tar according to embodiment of the present invention adds row's catalyst regeneration process outside hydrogen
Flow chart.
Fig. 2 is that boiling wood tar according to embodiment of the present invention adds the technology that catalyst regeneration process is arranged outside hydrogen
Method and route schematic diagram.
Specific implementation mode
Present inventor has found afterwards after extensive and in-depth study：On the one hand, wood tar itself is easy to condensation knot
It is burnt；On the other hand, since the presence of oxygen atom so that catalyst carried metal element is aoxidized during wood tar hydrogenation deoxidation
And inactivate, therefore catalyst life is only 1~2 week, traditional fixed bed is completely not applicable；Ebullated bed passes through to urging in reactor
The regular replacing section of agent, it is ensured that the catalyst in reactor is in the higher level of activity always, therefore is suitble to wooden burnt
The use of the hydrogenation deoxidation process of oil；But in wood tar hydrogenation process, fluidized bed reactor outer a large amount of inactivations arranged online
Catalyst is unable to get rational processing, and there are certain environmental risks；Meanwhile the catalyst after inactivation can not regenerate use,
So that wood tar adds hydrogen operating cost high；If may be implemented in ebullated bed wood tar hydrogenation technique outer lose work and urges
The on-line regeneration of agent can make the environment friendly that the outer waste discharge of device greatly reduces, improves technique admittedly, the fortune for reducing device
Row cost；Meanwhile decaying catalyst arrange outside during be that reactor is transported out by oil phase, so during outer row, also
A large amount of oil phase can be carried secretly, if realizing the recycling to these oil phases, moreover it is possible to more economic benefits are created, for this technology
Industrial application be of great significance.
In order to realize that the on-line regeneration of wood tar hydrogenation deoxidation decaying catalyst, inventor are considered first to ebullated bed wood
Catalyst is arranged outside hydrogenation of tar implements de-oiling to purify outer row's catalyst granules.Experimental studies have found that：For ebullated bed wood tar
The catalyst pulp oil content of hydrogenation process China and foreign countries row is up to 50~70% (in mass), by simply settling or mistake
Catalyst is arranged after filter effect, outside the oil-containing of gained and also contains oily 10~20% (in mass), can not be removed.The reason is that boiling
Rising catalyst used by a wood tar hydrogenation technique has great Kong Rong and specific surface area, while particle is with extremely complex
Receive, micro-structure surface and receive, micro-structure duct so that a large amount of high boiling range oil is present in oil-containing catalysis in the form of ADSORPTION STATE
In agent, it can not be desorbed since absorption oil is very strong with the adhesion strength of particle.It, can be compared with studies have shown that using the similar principle that mixes
Easily the oil extraction of ADSORPTION STATE is washed in organic solvent, achievees the purpose that de-oiling；The organic solvent of continuous phase is in eddy flow field
Stable eddy flow field can be formed so that the catalyst being in the Swirling Flow of this stabilization occurs around cyclone central shaft
Revolution motion and spinning motion around particle central axis, can strengthen de-oiling by the motor behavior of this two particles
Journey.Its principle is：(1) organic solvent extracts the substance that can be mixed in catalyst granules, and particle is in organic solvent shape
At eddy flow field high speed rotation and revolution be continuously updated the interface of catalyst granules and organic solvent, pass through interface
It constantly updates, strengthens the extraction process that solvent externally arranges soluble substance in catalyst；(2) height of particle in micro- eddy flow field is utilized
Insoluble material in outer row's catalyst granules is carried out mechanical stripping, migrated into solvent by fast rotation.Finally with shorter stream
Journey, lower energy consumption complete the deoiling treatment of externally row's catalyst, have regenerated condition.Meanwhile utilizing in eddy flow field
Grain revolution behavior, outer row's catalyst granules after being washed micro- eddy flow extraction is completed (extract from rich in solvent rich in solvent
Wash the organic solvent of rear oil-containing) in separate.The research of micro- eddy flow field is derived from micro- cyclone, and micro- cyclone usually refers in particular to revolve
The nominal diameter for flowing device is less than the cyclone of 50mm, is one of frontier development of cyclone separation process.
Secondly, it to the reduction process of catalyst is intermittently operated that inventor, which solves traditional autoclave reduction furnace, needs frequency
There is essential insecurity in the atmosphere in numerous replacing apparatus, develop a kind of revolution continuously restored to catalyst
Kiln plant.Using rotary kiln device, the outer row after micro- eddy flow extracts elution oil, organic solvent decrement is urged in a hydrogen atmosphere
Catalyst particles are restored so that the active metal reduction aoxidized on outer row's catalyst granules has activity again, can be with
It is back to fluidized bed reactor reuse.Rotary kiln device is in hydrogen reducing metal process, and catalyst granules is continuous and hydrogen
Gas comes into full contact with, and reduction efficiency is high, flow is short, and device continuous operation, operating condition are good.
Based on the studies above and discovery, the present invention is accomplished.
In the disclosure in a first aspect, providing the on-line regeneration side that a kind of ebullated bed wood tar adds hydrogen decaying catalyst
Method, this approach includes the following steps：
(A) it is arranged outside catalyst and strains oil：Oil is strained to implementing gravity by the outer catalyst pulp being discharged of fluidized bed reactor interval,
To isolate free oil；
(B) catalyst, lean solvent mixing：To in step (A) through sedimentation strain oil after gained catalyst granules and lean solvent
It is mixed with certain proportion, to form the homogeneous mixture of catalyst granules and lean solvent；
(C) micro- eddy flow extraction is washed:Micro- rotation is implemented to the homogeneous mixture of the catalyst granules of gained and lean solvent in step (B)
Stream is strengthened extraction and is washed so that and the oil phase that catalyst granules carries or sticks migrates into lean solvent, while being acted on using cyclonic separation,
Realize efficiently separating for de-oiling rear catalyst particle and rich solvent；
(D) solvent is reduced：The catalyst granules with organic solvent in step (C) after micro- eddy flow extraction is washed is implemented
Eddy flow is concentrated and is dried from returning charge, with the organic solvent that Removal of catalyst is carried secretly, organic solvent is avoided to run damage；
(E) solvent reclamation：Separation is implemented to the rich solvent obtained in step (C) using chemistry or physical separation means,
Lean solvent is obtained to be recycled with return to step (B) recycling and oil phase；And (F) metal reduction：In a hydrogen atmosphere
Catalyst granules after micro- eddy flow extracts elution oil, organic solvent decrement is restored so that on outer row's catalyst granules
Aoxidized active metal reduction, have activity again, so as to be back to fluidized bed reactor reuse.
In the disclosure, the oil content of the catalyst pulp of the outer discharge described in step (A) is 50~70% (with quality
Meter)；By straining oily process, the storage cushioning effect to the outer row's catalyst pulp of interval is also completed, oily rear catalyst particle is strained
Continuous processing can operate continuously its regenerative process.
In the disclosure, the catalyst used in the ebullated bed wood tar hydrogenation technique described in step (A) is activated carbon supported
Type catalyst, wherein active metallic element are iron, nickel, molybdenum or platinum.
In the disclosure, the lean solvent described in step (B) is methanol or ethyl alcohol, or can be with outer row's catalyst pulp
In the polar organic solvent that mixes of main oil phase component.
In the disclosure, the temperature of the homogeneous mixture of control catalyst granules and lean solvent is not higher than in step (B)
100℃。
In the disclosure, in step (B), the mixed proportion of catalyst granules and lean solvent is 1:1~1:50 (quality
Than), it mixes by stirring, the stirring residence time is 1~30min.
In the disclosure, the oil content of the de-oiling catalyst granules obtained after the step (C) and step (D) is less than
2%, dissolvent residual rate was less than for 0.1% (in mass).
In the disclosure, in step (F), the lower gold to being loaded on catalyst is enclosed in hydrogen atmosphere using rotary kiln device
Category is restored, and reduction temperature is 180~320 DEG C.
In the second aspect of the disclosure, provides a kind of ebullated bed wood tar and the on-line regeneration of hydrogen decaying catalyst is added to fill
It sets, which includes：
Buffering strains oil tank, for ebullated bed wood tar hydrogenation reactor, outer row's catalyst pulp to carry out gravitational settling online
Oil is strained to detach free oil, and realizes the buffer storage to catalyst pulp；
The screw feeder that tank bottom discharge port is connect is strained with buffering, for the catalyst granules strained obtained by oil will to be buffered
Continuously, auger tank is quantitatively inputted, to ensure that the regeneration treatment of catalyst can be carried out continuously；
Auger tank for straining catalyst granules obtained by oil to sedimentation and lean solvent mixes, and regulates and controls mixing
The temperature and liquid-solid ratio of object；
The solvent pump being connect with an entrance of auger tank, for lean solvent to be pumped into auger tank；
The booster pump being connect with the discharge port of auger tank, for the mixture in auger tank to be pumped into micro- eddy flow
Extraction is washed in device；
Device is washed with micro- eddy flow extraction of the outlet connection of booster pump, for providing stable micro- eddy flow field, utilizes catalyst particles
High speed autobiography and revolution behavior of the grain in micro- eddy flow field quickly update the interface enhancing extraction process of extraction, and are cut using fluid
Shear force realizes the mechanical stripping process to particle surface oil phase, to realize the de-oiling of catalyst granules；Meanwhile utilizing eddy flow field
Middle centrifugal force realizes efficiently separating for extraction rear catalyst particle and rich solvent；
The cyclone purifier that the rich solvent outlet connection at the top of device is washed with micro- eddy flow extraction washes device for removing micro- eddy flow extraction
The micro mist carried secretly in the rich solvent of top discharge；
The eddy flow decrement device that the de-oiling catalyst particle exit of device bottom is connect is washed with micro- eddy flow extraction, for being catalyzed to de-oiling
The organic solvent of agent entrainment implements removing；
Connect with cyclone purifier bottom and eddy flow decrement device bottom from returning charge drying machine, for realizing catalyst granules
The removing of residual organic solvents after de-oiling；
Pans are pre-processed with the catalyst from returning charge drying machine powder granule outlet connection, for storing urging after de-oiling
Agent is prepared for the regeneration treatment of catalyst；
The rotary kiln that the bottom discharge mouth of pans is connect is pre-processed with catalyst, in a hydrogen atmosphere to by micro-
Outer row's catalyst granules after eddy flow extraction elution oil, organic solvent decrement restores so that the quilt on outer row's catalyst granules
The active metal of oxidation restores, and has activity again, is reused so as to be back to fluidized bed reactor；
The cyclone dust collectors being connect with the gaseous phase outlet from returning charge drying machine, for removing from having from returning charge drying machine
The catalyst fines that solvent is mingled with；
It is reduced the top export of device with the top export of cyclone purifier, eddy flow and the top export of cyclone dust collectors is connect
Rectifying column, for the regeneration cycle of rich solvent；
The condenser being connected is exported with the top gaseous phase of rectifying column, for solvent vapo(u)r to be carried out condensing recovery；
The return tank of top of the tower being connected with the outlet of condenser, for storing condensate liquid, carrying out overhead reflux or directly obtaining
Organic solvent is obtained, is recycled；
The solvent pump being connected with the outlet of return tank of top of the tower, for using the part organic solvent in return tank of top of the tower as time
Flowing liquid is introduced into rectifying column；
The solvent pump being connected with the outlet of return tank of top of the tower, for stirring the part organic solvent blowback in return tank of top of the tower
It mixes in blending tank, realizes the circular regeneration of organic solvent；
The circulating pump being connected with the bottom of rectifying column is transported to for taking out partially liq from bottom of tower as liquid is boiled again
In reboil column；And
The reboil column being connected with circulating pump generates upflowing vapor for realizing the vaporization of liquid, realizes continuous rectification operation
Flow.
In the disclosure, the micro- eddy flow extraction wash device can be by more parallel connections, to meet the needs for the treatment of capacity；Micro- rotation
The inlet velocity that stream extraction washes device is not less than 8m/s；Import and oil-containing organic solvent outlet pressure drop≤0.15MPa；Top rich solvent
Export solid content≤5ppm；De-oiling catalyst particle exit flow in bottom is continuously adjustable, accounts for the 3~50% of inlet flow rate (with matter
Gauge).
Methods and apparatus of the present invention is suitable for ebullated bed wood tar and adds the regeneration method for arranging catalyst outside hydrogen, is also applied for
The processing and regeneration of the various oily wastes of the generations such as oil field, refinery.
Below referring to attached drawing.
Fig. 1 is the technique that boiling wood tar according to embodiment of the present invention adds row's catalyst regeneration process outside hydrogen
Flow chart.As shown in Figure 1, the online outer row's catalyst pulp of interval strains oil tank in buffering in ebullated bed wood tar hydrogenation process
It carries out straining oil to the gravitational settling of free oil in the slurry in 1, the free oil isolated strains 1 top discharge of oil tank from buffering；Together
When, mixing slowly for bottom is carried out in buffering strains oil tank 1, is sunk with preventing outer row's catalyst granules from straining 1 bottom of oil tank in buffering
Product is hardened；Sedimentation strain outer row's catalyst granules obtained by oil by screw feeder 2 act on it is continuous, quantitatively input auger tank
3, meanwhile, lean solvent is pumped into auger tank 3 after metering by solvent pump 16；By stirring to get in auger tank 3
The mixture of outer row's catalyst granules and lean solvent, and liquid-solid ratio is more adjusted, and regulate and control mixture according to used solvent
Temperature is to suitable；The mixture of outer row's catalyst granules and lean solvent is pumped into micro- eddy flow extraction from auger tank 3 by booster pump 4 and washes
In device 5, pass through the high speed rotation and revolution of particle in micro- eddy flow field so that inhaled in outer row's catalyst particle surface and internal gutter
Attached oil is continuously updated with the extraction interface of organic solvent, is adsorbed to strengthen in outer row's catalyst particle surface and internal gutter
Oil is extracted into the process of solvent；Meanwhile using the high speed revolution and rotation of particle in micro- eddy flow field, by centrifugal force by outer row
Insoluble material carries out mechanical stripping in catalyst granules, migrates into solvent, idetified separation；In extraction process, moreover it is possible to profit
Device 5 is washed with micro- eddy flow extraction and completes initial gross separation of the de-oiling catalyst granules with rich solvent, and the rich solvent and de-oiling for forming oil-containing are urged
Two strands of materials of catalyst particles (residual organic solvent)；Rich solvent washes the overflow port outflow at 5 top of device from micro- eddy flow extraction, into eddy flow
Clarifier 6 isolates a small amount of catalyst granules carried secretly in rich solvent, and purified rich solvent enters rectifying column 12, carries out molten
The separation of agent and oil, realizes the regeneration of solvent, and recycle isolated oil；De-oiling catalyst (residual organic solvent) first into
Enter eddy flow decrement device 7 and eddy flow concentration is carried out to the de-oiling catalyst washed by eddy flow extraction, removes having in most catalyst
Solvent；Catalyst granules by eddy flow concentration, which enters from returning charge drying machine 8, carries out finally dividing for de-oiling catalysts and solvents
From the de-oiling catalyst powder particle of gained, which drops into catalyst pretreatment pans 9, carries out buffer storage, is unloaded by star-like
Material valve enters in rotary kiln 10；Nitrogen is passed through simultaneously in catalyst pretreatment pans 9；The condensed water of gained is dried from from returning charge
It is discharged in machine 8；The reducing/regenerating of catalyst is carried out using hydrogen in rotary kiln 10, the hydrogen of gained is discharged from top, gained
Active catalyst from bottom be discharged；It is removed from the organic vapor of the drying gained of returning charge drying machine 8 by cyclone dust collectors 11
The a small amount of catalyst granules carried secretly in devaporation, subsequently into rectifying column 12；It is followed into the rich solvent in rectifying column in bottom of tower
Enter reboil column 18 under the action of ring pump 17, realize the vaporization of liquid, generate upflowing vapor, flow back into rectifying column 12, realizes
Continuous rectification operating process；The condensed water of gained is discharged；Heavy phase oil obtained by rectifying (desorption oil) is arranged through 12 outlet at bottom of rectifying column
Go out to enter the fixed bed reactors of next step, and the solvent vapo(u)r of light phase is flowed out from 12 top of rectifying column, condensed device 13 enters
In return tank of top of the tower 14, the solvent part in return tank of top of the tower 14 is flowed back into through solvent pump 15 in rectifying column 12, for condensing
Liquid in tower, part cycle solvent are flow back into through solvent pump 16 in auger tank 3, realize the circular regeneration application of solvent；
Fixed gas is discharged.
Fig. 2 is that boiling wood tar according to embodiment of the present invention adds the technology that catalyst regeneration process is arranged outside hydrogen
Method and route schematic diagram.As shown in Fig. 2, the outer row's catalyst being discharged from fluidized bed reactor strains oil by buffering removes big portion
Then the free oil divided washes away the capillary oil and hole oil of Catalyst Adsorption, gained under the effect of washing of micro- eddy flow of lean solvent extraction
Rich solvent pass through solvent reclamation, obtain being detached from oil and lean solvent, lean solvent is carried out back to previous step to straining oily rear catalyst
Extraction is washed, and the catalyst (residual organic solvent) after micro- eddy flow extraction is washed can remove the organic molten of deentrainment by solvent decrement
Agent obtains dry catalyst granules, is restored by metal so that the metal aoxidized possesses activity again, realizes catalyst
Regeneration, can return fluidized bed reactor recycling.
Embodiment
With reference to specific embodiment, the present invention is further explained.It should be appreciated, however, that these embodiments are only used for
It is bright the present invention and be not meant to limit the scope of the invention.The test method of actual conditions is not specified in the following example, usually
According to normal condition, or according to the normal condition proposed by manufacturer.Unless otherwise indicated, all percentage and number be by weight
Meter.
Embodiment 1：
For catalyst regeneration process technique is arranged outside the ebullated bed wood tar hydrogenation plant of 30,000 tons/year of scales, according to this hair
Bright method adds row's catalyst progress outside hydrogen micro- in ebullated bed wood tar first using methanol (64.7 DEG C of boiling point) as solvent
Eddy flow extraction is washed；Solvent decrement then is carried out to the catalyst granules of de-oiling and removes organic solvent, obtains dry catalyst granules,
Hydrogen reducing is carried out to the metallic particles of inactivation subsequently into rotary kiln, realizes the regeneration of catalyst, back in ebullated bed
It is recycled；Extract the regeneration that the rich solvent after washing carries out solvent by rectifying, isolates desorption oil, solvent returns after regeneration
Section is washed to micro- eddy flow extraction to recycle, specific operation and effect are described as follows：
1. ebullated bed wood tar adds the property for arranging catalyst outside hydrogen
Catalyst pulp is arranged outside oil-containing to be intermittently discharged from reactor, per row oil-containing catalyst 720kg beyond the highest heavens,
In：
Oil content is 60 weight %, and the key component of oil phase is：(1) aromatic hydrocarbons 46.44%, (2) alkane 35.09%, (3) benzene
Phenol 8.56%, remaining includes alkene, ether, ester, ketone, alcohol, water etc.；
Ebullated bed wood tar, which adds, arranges catalyst fresh carrier as active carbon particle outside hydrogen, have flourishing gap structure,
BET specific surface area is 800~1000m2/ g, grain diameter are 1~2mm, and metal conduct is adsorbed in activated carbon surface and gap
Catalytic active component.
2. implementation process
It is as follows with reference to the specific implementation step of the present invention：
(i) ebullated bed wood tar adds row's catalyst pulp outside hydrogen to be intermittently stored in buffering with the outer discharge capacity of daily 720kg
It strains in oil tank, straining oil by gravitational settling detaches the free oil in the slurry, meanwhile, carry out bottom in buffering strains oil tank
Mix slowly, with prevent outer row's catalyst granules buffering strain tank bottom deposition it is hardened.
(ii) using screw feeder by the buffered outer row's catalyst (18.3 weight % of oil-containing) strained after oil with 14.7kg/
The rate of h continuously inputs in auger tank, meanwhile, cycle solvent methanol is pumped into 2000kg/h in auger tank, is formed
The mixture of a certain proportion of catalyst and methanol, stirs evenly, and regulating and controlling temperature is to suitable.
(iii) agitated mixed catalyst and methyl alcohol mixed liquor are pumped into micro- eddy flow extractor using booster pump
(flow 2014.7kg/h) passes through the high speed rotation and revolution of particle in micro- eddy flow field so that arrange catalyst particle surface outside
It is continuously updated with the extraction interface of methanol with oil is adsorbed in internal gutter, to strengthen outer row's catalyst particle surface and inside
The process that oil is extracted into methanol is adsorbed in duct；Meanwhile using in micro- eddy flow field particle high speed revolution and rotation, by from
Insoluble material in outer row's catalyst granules is carried out mechanical stripping by mental and physical efforts, is migrated into methanol, idetified separation.In extraction process
In, also device is washed using micro- eddy flow extraction and complete de-oiling catalyst granules with the initial gross separation of the rich solvent of methanol, form oil-containing
Two strands of materials of methanol rich solvent and de-oiling catalyst granules (residual organic solvent), methanol rich solvent are washed from micro- eddy flow extraction at the top of device
Overflow port outflow, de-oiling catalyst (residual organic solvent) from micro- eddy flow extraction wash device bottom underflow opening outflow.
(iv) the methanol rich solvent of the oil-containing enters cyclone purifier, isolates carried secretly in methanol rich solvent a small amount of and urges
Catalyst particles, purified methanol rich solvent enter rectifying column from cyclone purifier top overflow port, carry out point of solvent and oil
From realizing the regeneration of methanol solvate, and recycle isolated oil.
(v) de-oiling catalyst (residual organic solvent) described in step (iii) initially enters eddy flow decrement device, to through overwinding
The de-oiling catalyst that stream extraction is washed carries out eddy flow concentration, removes the most of methanol carried secretly in catalyst, the methanol after eddy flow concentration
Rich solvent enters rectifying column from eddy flow decrement device top overflow port.
(vi) catalyst granules for passing through eddy flow concentration enters from returning charge drying machine progress de-oiling catalysts and solvents most
Separation eventually, wherein steam drying temperature are 160 DEG C, and gained de-oiling catalyst powder particle drops into catalyst pretreatment pans
Middle carry out buffer storage, dry gained methanol steam isolate a small amount of catalyst powder of entrainment by cyclone dust collectors, then
Into in rectifying column.
(vii) entered in rotary kiln by star-shaped discharge valve by the catalyst granules dried from returning charge, in rotary kiln
The reducing/regenerating of catalyst is carried out using hydrogen, temperature is 380 DEG C in rotary kiln, and pressure is -0.005MPa, the regeneration after reduction
Catalyst can be returned directly to recycle in hydrogenation reactor.
(viii) rich solvent entered in rectifying column enters reboil column under the action of the circulating pump of bottom of tower, realizes the vapour of liquid
Change, generate upflowing vapor, flow back into rectifying column, realizes continuous rectification operating process.Heavy phase oil is through rectifying column bottom obtained by rectifying
Portion exports the fixed bed reactors for being discharged into next step, and the solvent vapo(u)r of light phase flows out at the top of rectifying column, condensed device
Into in overhead reflux device, the solvent part in overhead reflux device is flowed back into through solvent pump in rectifying column, in condensing tower
Liquid, a part are flow back into through solvent pump in auger tank, realize the circular regeneration application of solvent.
3. interpretation of result
3.1 oily recovering states：
Ebullated bed wood tar adds row's catalyst outside hydrogen to pass through gravity per catalyst 720kg, wherein oil-containing 432kg is arranged beyond the highest heavens
Sedimentation strains oily recyclable free oil 367.2kg/ days.It uses methanol to be washed for extraction and externally arranges the micro- eddy flow of catalyst implementation with organic solvent
Extraction is washed, and the oil content for extracting outer row's catalyst granules after washing drops to 1.88%, and the overall recovery efficiency of oil is reached
98.7%.
After each step is implemented, the material composition of outer row's catalyst see the table below shown in 1：
1 ebullated bed wood tar of table adds the material composition that catalyst is arranged outside hydrogen after each step
The recovery of 3.2 catalyst activities
Oil removing rear catalyst particle oil content be no more than 2%, solvent content be no more than 0.1% (in mass), into return
In rotary kiln, the active metal aoxidized on catalyst granules is had activity, is back to ebullating bed reactor again by hydrogen reducing
Device is reused, and the 80% of activation recovering to fresh catalyst.
Above-mentioned listed embodiment is only the preferred embodiment of the disclosure, not is used for limiting the implementation model of the disclosure
It encloses.Equivalence changes and modification made by i.e. all contents according to the application the scope of the claims, all should be the technology scope of the disclosure.
It is incorporated herein by reference in all documents that the disclosure refers to, it is independent just as each document
It is incorporated as with reference to such.In addition, it should also be understood that, after having read the above-mentioned instruction content of the disclosure, those skilled in the art can
To be made various changes or modifications to the disclosure, such equivalent forms equally fall within model defined by the application the appended claims
It encloses.
Claims (10)
1. a kind of ebullated bed wood tar adds the on-line regeneration method of hydrogen decaying catalyst, this approach includes the following steps：
(A) it is arranged outside catalyst and strains oil：The catalyst pulp being externally discharged implements gravity and strains oil, to isolate free oil；
(B) catalyst, lean solvent mixing：To the catalyst granules of gained and lean solvent carry out after oil is strained in sedimentation in step (A)
Mixing, to form the homogeneous mixture of catalyst granules and lean solvent；
(C) micro- eddy flow extraction is washed:It is strong that micro- eddy flow is implemented to the homogeneous mixture of the catalyst granules of gained and lean solvent in step (B)
Change extraction to wash so that the oil phase that catalyst granules carries or sticks migrates into lean solvent, while acting on using cyclonic separation, realizes
The separation of de-oiling rear catalyst particle and rich solvent；
(D) solvent is reduced：The catalyst granules with organic solvent obtained after micro- eddy flow extraction is washed in step (C) is implemented
Eddy flow is concentrated and is dried from returning charge, with the organic solvent of Removal of catalyst particle entrainment；
(E) solvent reclamation：Separation is implemented to the rich solvent obtained in step (C), obtain lean solvent is made with return to step (B) cycle
With and oil phase recycled；And
(F) metal restores：Catalyst granules after micro- eddy flow extracts elution oil, organic solvent decrement is restored so that
The active metal reduction aoxidized on outer row's catalyst granules, has activity again.
2. the method as described in claim 1, which is characterized in that in step (A), the catalyst pulp of the outer discharge is by boiling
The outer row of reactor interval is risen, oil content is 50~70%, in mass；By straining oily process, also complete outer to interval
Arrange the storage cushioning effect of catalyst pulp.
3. method as claimed in claim 1 or 2, which is characterized in that in step (A), the ebullated bed wood tar adds hydrogen work
Skill used catalyst is activated carbon supported type catalyst, and wherein active metallic element is iron, nickel, molybdenum or platinum.
4. the method as described in claim 1, which is characterized in that in step (B), the lean solvent be methanol or ethyl alcohol, or
The polar organic solvent that person mixes with the main oil phase component in the catalyst pulp of outer discharge.
5. method as described in claim 1 or 4, which is characterized in that in step (B), catalyst granules and lean solvent it is mixed
Composition and division in a proportion example is 1:1~1:50, by quality ratio；It mixes by stirring, the stirring residence time is 1~30min；Control catalyst particles
The temperature of the homogeneous mixture of grain and lean solvent is not higher than 100 DEG C.
6. the method as described in claim 1, which is characterized in that the de-oiling catalysis obtained after the step (C) and step (D)
The oil content of agent particle is less than 2%, dissolvent residual rate and is less than 0.1%, in mass.
7. the method as described in claim 1, which is characterized in that in step (E), using chemistry or physical separation means pair
The rich solvent obtained in step (C) implements separation.
8. the method as described in claim 1, which is characterized in that in step (F), gone back in hydrogen atmosphere using rotary kiln
Original, reduction temperature are 180~320 DEG C；Active metal through reduction is back to fluidized bed reactor reuse.
9. a kind of ebullated bed wood tar adds the on-line regeneration facility of hydrogen decaying catalyst, which includes：
Buffering strains oil tank (1), and the catalyst pulp for being externally discharged implements gravity and strains oil, to isolate free oil, and realizes
To the storage buffering of catalyst pulp；
The auger tank (3) that oil tank (1) is connect is strained with buffering, for the catalyst granules and poor to the gained after oil is strained in sedimentation
Solvent is mixed, to form the homogeneous mixture of catalyst granules and lean solvent, and regulate and control mixture temperature and liquid it is solid
Than；
The micro- eddy flow extraction being connect with auger tank (3) washes device (5), for the uniform of the catalyst granules of gained and lean solvent
Mixture is implemented micro- eddy flow reinforcing extraction and is washed so that the oil phase that catalyst granules carries or sticks migrates into lean solvent, while profit
It is acted on cyclonic separation, realizes the separation of de-oiling rear catalyst particle and rich solvent；
Wash the eddy flow decrement device (7) that device (5) connect with micro- eddy flow extraction, and connect with eddy flow decrement device (7) from returning charge drying
Machine (8), for implementing eddy flow concentration to the catalyst granules with organic solvent obtained after micro- eddy flow extraction is washed and returning certainly
Drying is expected, with the organic solvent of Removal of catalyst particle entrainment；
The rectifying column (12) being connect with from returning charge drying machine (8), for implementing separation to obtained rich solvent, obtain lean solvent with
It recycles and oil phase is recycled；And
The rotary kiln (10) being connect with from returning charge drying machine (8), for after micro- eddy flow extracts elution oil, organic solvent decrement
Catalyst granules restored so that the active metal reduction aoxidized on outer row's catalyst granules has activity again.
10. device as claimed in claim 9, which is characterized in that micro- eddy flow extraction washes device (5) by more parallel connections, to meet
The demand for the treatment of capacity；Inlet velocity is not less than 8m/s；Import and oil-containing organic solvent outlet pressure drop≤0.15MPa；Top is rich
Solvent outlet solid content≤5ppm；De-oiling catalyst particle exit flow in bottom is continuously adjustable, accounts for the 3~50% of inlet flow rate,
In mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810551650.3A CN108704672A (en) | 2018-05-31 | 2018-05-31 | Ebullated bed wood tar adds the on-line regeneration method and apparatus of hydrogen decaying catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810551650.3A CN108704672A (en) | 2018-05-31 | 2018-05-31 | Ebullated bed wood tar adds the on-line regeneration method and apparatus of hydrogen decaying catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108704672A true CN108704672A (en) | 2018-10-26 |
Family
ID=63871139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810551650.3A Pending CN108704672A (en) | 2018-05-31 | 2018-05-31 | Ebullated bed wood tar adds the on-line regeneration method and apparatus of hydrogen decaying catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108704672A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110003937A (en) * | 2019-04-26 | 2019-07-12 | 上海华畅环保设备发展有限公司 | Boiling bed hydrogenation method |
| CN109999729A (en) * | 2019-04-26 | 2019-07-12 | 上海华畅环保设备发展有限公司 | Boiling bed hydrogenation catalyst reactor online eddy flow method for activation recovering in situ and device |
| CN110052226A (en) * | 2019-04-26 | 2019-07-26 | 上海华畅环保设备发展有限公司 | Boiling bed hydrogenation catalyst reactor online eddy flow method for activation recovering in situ and device |
| CN110102226A (en) * | 2019-04-26 | 2019-08-09 | 河南百优福生物能源有限公司 | Particle removes technique and device in a kind of biomass pyrolysis liquid fluidized bed reactor |
| CN110129089A (en) * | 2019-04-26 | 2019-08-16 | 上海华畅环保设备发展有限公司 | Boiling bed hydrogenation method |
| CN110387261A (en) * | 2019-07-03 | 2019-10-29 | 国家能源集团宁夏煤业有限责任公司 | The processing unit and processing method of Fischer-Tropsch slag wax |
| CN111804311A (en) * | 2020-06-24 | 2020-10-23 | 河南神马尼龙化工有限责任公司 | Method for continuously maintaining performance of catalyst for cyclohexene production |
| CN112791669A (en) * | 2020-12-31 | 2021-05-14 | 华东理工大学 | Catalyst on-line rotational flow activity recovery method and device in C5 petroleum resin production |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4661265A (en) * | 1985-09-30 | 1987-04-28 | Amoco Corporation | Catalyst deoiling process |
| US4698321A (en) * | 1981-10-21 | 1987-10-06 | Georgia Tech Research Corporation | Regeneration of HDS catalysts |
| JP2008290071A (en) * | 2007-04-27 | 2008-12-04 | Cosmo Oil Co Ltd | Method for manufacturing catalyst for hydrotreating hydrocarbon oil and regeneration method |
| US20090110620A1 (en) * | 2005-07-29 | 2009-04-30 | Marcantonio Paul J | Process for metals recovery from spent catalyst |
| CN101475818A (en) * | 2009-01-23 | 2009-07-08 | 华东理工大学 | Coal tar coupled rotational flow purification method and apparatus |
| CN101485947A (en) * | 2008-12-30 | 2009-07-22 | 华东理工大学 | Method and device for removing micro-phase alkaline matter in fluid |
| CN101734834A (en) * | 2009-12-29 | 2010-06-16 | 新疆油田勘察设计研究院 | Method for recovering sandy oil-containing sludge |
| CN101962560A (en) * | 2010-09-29 | 2011-02-02 | 神华集团有限责任公司 | Extraction method of direct coal liquefaction residues and application of extracts |
| CN102050556A (en) * | 2009-10-30 | 2011-05-11 | 中国石油天然气股份有限公司 | Treatment method of oily sludge |
| CN102399564A (en) * | 2011-09-30 | 2012-04-04 | 神华集团有限责任公司 | System and method for treating coal direct liquefaction residue |
| CN102399565A (en) * | 2011-09-30 | 2012-04-04 | 神华集团有限责任公司 | Method for extracting heavy liquefied oil from residue of coal direct liquefaction, extracted heavy liquefied oil, and application thereof |
| CN102698815A (en) * | 2012-05-11 | 2012-10-03 | 上海华畅环保设备发展有限公司 | Method for treating boiling bed residue oil hydrogenating-discharged catalyst and device thereof |
| CN102698818A (en) * | 2012-06-21 | 2012-10-03 | 上海华畅环保设备发展有限公司 | Processing method and processing device for graded desorption of residue hydrotreating excretion catalyst in ebullated bed |
| CN103922499A (en) * | 2014-04-29 | 2014-07-16 | 华东理工大学 | Cyclone enhanced extraction method for heavy metal ions in waste water, and device thereof |
| CN105016949A (en) * | 2015-07-29 | 2015-11-04 | 上海米素环保科技有限公司 | Method and device for deep methanol removal from C4 |
| CN107227170A (en) * | 2017-07-27 | 2017-10-03 | 华东理工大学 | The system of sulfide in a kind of eddy flow reinforcing removing oil product |
-
2018
- 2018-05-31 CN CN201810551650.3A patent/CN108704672A/en active Pending
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4698321A (en) * | 1981-10-21 | 1987-10-06 | Georgia Tech Research Corporation | Regeneration of HDS catalysts |
| US4661265A (en) * | 1985-09-30 | 1987-04-28 | Amoco Corporation | Catalyst deoiling process |
| US20090110620A1 (en) * | 2005-07-29 | 2009-04-30 | Marcantonio Paul J | Process for metals recovery from spent catalyst |
| JP2008290071A (en) * | 2007-04-27 | 2008-12-04 | Cosmo Oil Co Ltd | Method for manufacturing catalyst for hydrotreating hydrocarbon oil and regeneration method |
| CN101485947A (en) * | 2008-12-30 | 2009-07-22 | 华东理工大学 | Method and device for removing micro-phase alkaline matter in fluid |
| CN101475818A (en) * | 2009-01-23 | 2009-07-08 | 华东理工大学 | Coal tar coupled rotational flow purification method and apparatus |
| CN102050556A (en) * | 2009-10-30 | 2011-05-11 | 中国石油天然气股份有限公司 | Treatment method of oily sludge |
| CN101734834A (en) * | 2009-12-29 | 2010-06-16 | 新疆油田勘察设计研究院 | Method for recovering sandy oil-containing sludge |
| CN101962560A (en) * | 2010-09-29 | 2011-02-02 | 神华集团有限责任公司 | Extraction method of direct coal liquefaction residues and application of extracts |
| CN102399564A (en) * | 2011-09-30 | 2012-04-04 | 神华集团有限责任公司 | System and method for treating coal direct liquefaction residue |
| CN102399565A (en) * | 2011-09-30 | 2012-04-04 | 神华集团有限责任公司 | Method for extracting heavy liquefied oil from residue of coal direct liquefaction, extracted heavy liquefied oil, and application thereof |
| CN102698815A (en) * | 2012-05-11 | 2012-10-03 | 上海华畅环保设备发展有限公司 | Method for treating boiling bed residue oil hydrogenating-discharged catalyst and device thereof |
| CN102698818A (en) * | 2012-06-21 | 2012-10-03 | 上海华畅环保设备发展有限公司 | Processing method and processing device for graded desorption of residue hydrotreating excretion catalyst in ebullated bed |
| CN103922499A (en) * | 2014-04-29 | 2014-07-16 | 华东理工大学 | Cyclone enhanced extraction method for heavy metal ions in waste water, and device thereof |
| CN105016949A (en) * | 2015-07-29 | 2015-11-04 | 上海米素环保科技有限公司 | Method and device for deep methanol removal from C4 |
| CN107227170A (en) * | 2017-07-27 | 2017-10-03 | 华东理工大学 | The system of sulfide in a kind of eddy flow reinforcing removing oil product |
Non-Patent Citations (1)
| Title |
|---|
| 广西壮族自治区地方志编纂委员会编: "《广西通志 有色金属工业志》", 31 December 1994, 南宁：广西人民出版社 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110003937A (en) * | 2019-04-26 | 2019-07-12 | 上海华畅环保设备发展有限公司 | Boiling bed hydrogenation method |
| CN109999729A (en) * | 2019-04-26 | 2019-07-12 | 上海华畅环保设备发展有限公司 | Boiling bed hydrogenation catalyst reactor online eddy flow method for activation recovering in situ and device |
| CN110052226A (en) * | 2019-04-26 | 2019-07-26 | 上海华畅环保设备发展有限公司 | Boiling bed hydrogenation catalyst reactor online eddy flow method for activation recovering in situ and device |
| CN110102226A (en) * | 2019-04-26 | 2019-08-09 | 河南百优福生物能源有限公司 | Particle removes technique and device in a kind of biomass pyrolysis liquid fluidized bed reactor |
| CN110129089A (en) * | 2019-04-26 | 2019-08-16 | 上海华畅环保设备发展有限公司 | Boiling bed hydrogenation method |
| CN109999729B (en) * | 2019-04-26 | 2022-08-02 | 上海华畅环保设备发展有限公司 | Method and device for recovering in-situ online rotational flow activity of catalyst in fluidized bed hydrogenation reactor |
| CN110387261A (en) * | 2019-07-03 | 2019-10-29 | 国家能源集团宁夏煤业有限责任公司 | The processing unit and processing method of Fischer-Tropsch slag wax |
| CN110387261B (en) * | 2019-07-03 | 2021-10-22 | 国家能源集团宁夏煤业有限责任公司 | Fischer-Tropsch wax residue treatment device and treatment method |
| CN111804311A (en) * | 2020-06-24 | 2020-10-23 | 河南神马尼龙化工有限责任公司 | Method for continuously maintaining performance of catalyst for cyclohexene production |
| CN111804311B (en) * | 2020-06-24 | 2023-09-22 | 河南神马尼龙化工有限责任公司 | Method for continuously maintaining performance of catalyst for cyclohexene production |
| CN112791669A (en) * | 2020-12-31 | 2021-05-14 | 华东理工大学 | Catalyst on-line rotational flow activity recovery method and device in C5 petroleum resin production |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108704672A (en) | Ebullated bed wood tar adds the on-line regeneration method and apparatus of hydrogen decaying catalyst | |
| CN107597201B (en) | Oil-containing outlet catalyst treatment and sorting reuse method and device | |
| CN103074097B (en) | Method and system for direct coal liquefaction | |
| CA2872696C (en) | Process and device for treating catalyst discharged from bubbling bed hydrogenation of residual oil | |
| CN102134643A (en) | Metal recovery from hydroconverted heavy effluent | |
| US7419608B2 (en) | Treating method and equipment for coke-cooling wastewater | |
| CN102698818B (en) | Processing method and processing device for graded desorption of residue hydrotreating excretion catalyst in ebullated bed | |
| WO2014000501A1 (en) | Combined filtering process for recycling precious metal from fischer-tropsch synthetic product | |
| CN108704673A (en) | Ebullated bed wood tar adds the de-oiling method and device of the outer waste discharge catalyst of hydrogen | |
| CN102807884B (en) | Method for preparing biological oil and biological char by thermal cracking and liquefying bamboo wood | |
| CN102399566A (en) | Method for extracting heavy liquefied oil and kerite substance from residue of direct coal liquefaction | |
| CN103282464A (en) | Hydrocracking process of heavy hydrocarbon distillates using supercritical solvent | |
| CN105061165A (en) | Reaction apparatus for preparing polyoxymethylene dimethyl ether | |
| JPH01131297A (en) | Treatment of heavy oil | |
| CN106190318A (en) | A kind of Processes and apparatus of coke gasification | |
| CN106635152B (en) | A kind of processing method of full fraction of coal tar oil | |
| WO2010045769A1 (en) | Method and device for short-flow desulfurizing recyled hydrogen | |
| CN103877958B (en) | For preparing the catalyst and preparation method of biodiesel and the preparation technology of biodiesel | |
| CN110205157A (en) | A kind of method of solid catalyst in removing catalytic cracked oil pulp | |
| JP5827753B2 (en) | An improved method for producing low ash refined coal from high ash coal while recovering total solvent | |
| CN110102226A (en) | Particle removes technique and device in a kind of biomass pyrolysis liquid fluidized bed reactor | |
| CN107674694A (en) | The method and device that a kind of junked tire cracking recycles | |
| CN104673356B (en) | Oily waste water Catalyst processing method is arranged outside a kind of ebullated bed | |
| CN102603539A (en) | Method and device for recycling catalyst particles in crude toluene diamine | |
| WO2012079499A1 (en) | Method and device for enclosed recycling of oil-water-sludge in oil shale dry distillation system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181026 |
|
| RJ01 | Rejection of invention patent application after publication |