CN110479387A - One kind is for solid-phase catalyst cleaning and regeneration method in catalyst liquid-solid reaction system - Google Patents
One kind is for solid-phase catalyst cleaning and regeneration method in catalyst liquid-solid reaction system Download PDFInfo
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- CN110479387A CN110479387A CN201910823382.0A CN201910823382A CN110479387A CN 110479387 A CN110479387 A CN 110479387A CN 201910823382 A CN201910823382 A CN 201910823382A CN 110479387 A CN110479387 A CN 110479387A
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- 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
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- 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
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- 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
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- 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
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- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
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Abstract
The present invention provides one kind for solid-phase catalyst cleaning and regeneration method in catalyst liquid-solid reaction system, reaction solution and the solid catalyst being contaminated are sent into film filter sheath and wash system, cleaned by classification by this method, control set washes temperature, and surface of solids organic matter is desorbed.Clear liquid is formed, clear liquid enters the separation that downstream process carries out organic matter and solvent containing the solvent that organic matter is desorbed by filter membrane by membrane filtration system.It is cleaned clean catalyst solid, Returning reacting system.The solid catalyst inactivated because surface is contaminated can be carried out effective regeneration by method provided by the invention；Compared with published catalytic hydrogenation method, this method is simple and effective, at low cost, and economy is high, reduces the loss of catalyst, and synthesis improves economic benefit.
Description
Technical field
The present invention relates to a kind of method of solid-phase catalyst clean and reuse in catalyst solid-liquid reaction system, more particularly, to
A method of solid-phase catalyst clean and reuse in catalyst solid-liquid reaction system is carried out by membrane filtration module.
Background technique
Reactant is reacted by the catalyst particles being suspended in liquid phase in slurry-phase reactor.Catalyst particle size is logical
Often between 10~1000 μm, it is suspended in liquid phase by air-flow bubbling or mechanical stirring, for liquid-solid catalytic reaction, with anti-
Lengthening between seasonable, wetability good catalyst surface can thereby reduce reaction raw materials accompanying by reaction product, by-product
The area contacted with catalyst.To reduce the conversion ratio of reaction, selectivity.It just needs to carry out solid after this operating condition occurs
Catalyst wash regeneration.
Domestic 105728035 B of patent CN is disclosed by the way that decaying catalyst is passed through vapor and oxygen at low temperature
Catalyst is carried out to the step of hydro-thermal process after the step of carrying out low-temperature bake and low-temperature bake using the acid solution containing metal salt
Suddenly.It can be realized and remove the impurity blocked in catalyst duct and repair skeleton structure, pass through simple technique and cost control
Decaying catalyst activation recovering can be made to fresh dose of level, the service life also can reach more than half level of fresh catalyst.
Catalyst regeneration is carried out using low-temperature bake method in above-mentioned patent, needs to carry out solid-liquor separation, is burned, to equipment
It is more demanding, it is complicated for operation, and liquid is difficult to be completely separated admittedly, causes the loss in roasting process to chemicals.Roasting is to catalysis
The badly broken of agent causes more losses of catalyst.Lack of gas are discharged after roasting simultaneously, it is also necessary to environmental protection measure ability be arranged
Reach discharge standard.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of simple and convenient, good economy performance catalyst regeneration process, it can be real
Existing simple operations, micro loss carry out catalyst regeneration under the operating condition of no exhaust gas outlet.
In order to achieve the above objectives, the technical solution of the invention is achieved in that
For one kind for solid-phase catalyst cleaning and regeneration method in catalyst liquid-solid reaction system, this method will be solid containing inactivation
The reaction solution of body catalyst is sent into film filter regeneration system, is washed by being classified set, the organic matter of solid catalyst surface is taken off
It is attached, realize catalyst regeneration.
Further, cleaning and regeneration method includes the following steps:
Step 1: the reaction solution containing decaying catalyst enters level-one membrane filtration module from reaction kettle extraction by primary pump,
The separation for realizing catalyst and reaction product, obtains reaction product and the dope containing catalyst, wherein reaction product enters product
Rectification working process is post-processed, the dope containing catalyst enters level 2 buffering tank；
Step 2: the dope containing catalyst that step 1 obtains enters level 2 buffering tank and mixes with clear liquid, and obtained mixing is molten
Liquid is pumped into secondary membrane component by second level, by the isolated dope containing catalyst of secondary membrane component and clearly
Liquid, clear liquid enter product post-processing rectification working process or return to reaction kettle；
Step 3: the dope containing catalyst that step 2 obtains enters three-level surge tank and mixes with clear liquid, and obtained mixing is molten
Liquid is pumped into three-level membrane filtration module by three-level, by the isolated dope containing catalyst of three-level membrane filtration module and clearly
Liquid；
Step 4: repeating step 3 until n-1 grades；
The dope containing catalyst that 5:n-1 grades of membrane filtration modules of step are filtered enters n grades of surge tanks and mixes with clear liquid, obtains
Mixed solution a part be pumped into n grades of membrane filtration modules by n grade, it is isolated containing catalyst by n grades of membrane filtration modules
Dope and clear liquid, the isolated dope containing catalyst of n grades of membrane filtration modules returns to n grades of surge tanks, in n grades of surge tanks
Another part mixed solution is pumped into regeneration kettle；
Step 6: being continuously added to fresh solvent in Xiang Zaisheng kettle, and solvent is heated, using fresh solvent to urging
Agent carries out boiling.Regenerative mixed solution is continuously extracted out from regeneration kettle, is sent into n+1 grades of membrane filtration modules through supercooling, is passed through
UF membrane obtains clear liquid and regenerated catalyst；
In step 1 to step 6, grade membrane filtration module from three-level membrane filtration module to n+1, membrane filtration modules at different levels are separated
To clear liquid return in upper level surge tank and mixed with the dope containing catalyst.
Classification set, which is washed, refers to step 1 to the cleaning method described in step 6.The first order set system of washing includes primary pump and level-one
Membrane filtration module；Second level set washes the buffering that every level-one set that system covers system of washing to n-th grade washes system and include appropriate level
Tank, pump and membrane filtration module；It includes regeneration kettle, pump and membrane filtration module that (n+1)th grade of set, which washes system,.
In above-mentioned cleaning process, main catalyst pulp (dope containing catalyst) washes system to last from first order set
Level-one set washes system orientation flowing, and main solvent (fresh solvent or clear liquid) is washed system from afterbody set and washed to first order set
System flow, dominant catalyst slurry is contrary with main solvent flow, and such design need to only be added new in afterbody
Fresh solvent can be realized multistage set and wash, can not only promote cleaning effect, can also save significantly on solvent, reduce cost, has good
Economic benefit.
It is regenerated if directly being heated catalyst with fresh solvent, the operation of one-pot single batch is belonged under this operating condition, single batch
Washing, the heating boiling of single batch cannot keep continuous discharge for the catalyst Returning reacting system after regeneration.If guaranteed again
The raw continuous Returning reacting system of catalyst, it is necessary to which more regeneration kettles (operation temperature is high, and operating pressure is high) is set.Simultaneously because
Single-stage cleaning can not be switched to online in next stage cleaning, it is necessary to be separated catalyst and washed solvent, then with big
Amount solvent cleaning multipass just can guarantee the effect of catalyst wash in this case.And this set is washed technique and is washed using classification set,
It can be realized on-line continuous extraction spent catalyst, cleaned, the catalyst energy subsequently into regeneration kettle regeneration, after regenerating
Enough continuous Returning reacting systems.
And in above-mentioned cleaning method, multistage set washes the pollutant that can effectively remove catalyst surface, and regeneration kettle high temperature adds
Heat can be such that the small organic matter retained in catalytic inner gap releases, to realize the thorough regeneration of catalyst, and only
Fresh solvent need to be added in regeneration kettle, therefore catalyst first passes around after multistage set washes, then passes through regeneration kettle high temperature regeneration, a side
Face can save a large amount of solvents, on the other hand be remarkably improved cleaning and regeneration effect, and regenerated catalyst without interruption returns to reaction system
System.
Regeneration kettle carries out catalysed particulate internal washing using thermophilic digestion mode, and the solvent of high temperature will cause high pressure, to
Catalyst pulp is directly entered regeneration kettle after membrane filtration module, then needs to improve the lift of pump, and then can waste electricity.By
It is smaller in the catalyst slurry doses for entering regeneration kettle, using the pump of an independent low-flow high-lift, it can be effectively reduced fortune
Row cost.
Further, dope a part containing catalyst that level-one membrane filtration module to n-1 grades of membrane filtration modules are filtered is returned
It returns reaction kettle or with level-one surge tank, dope of the another part containing catalyst enters next stage surge tank.A certain amount of catalyst
Slurry recycles between surge tank and membrane filtration module, it is possible to provide certain crossflow velocity and membrane flux, to guarantee that film filters
Go on smoothly.
Further, for solid catalyst by multistage membrane filtration module cleaning, it is 3,4 ,~20 that the set, which washes series n,.It is excellent
Selection of land, it is 3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20 that set, which washes series,.
Further, the membrane filtration module is ceramic film component or other inorganic membrane assemblies.
Further, the recoil cleaning of the membrane filtration module uses the pulse of moment high back voltage, and uses methanol conduct
Backflushing medium.
Further, the fresh solvent selects pure methanol solution.
Further, in the step 6, regeneration kettle heating temperature is 100~200 DEG C.Preferably, kettle heating temperature is regenerated
It is 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C or 200 DEG C.
Further, in the step 6, regenerative mixed solution is sent into the cooling temperature before afterbody membrane filtration module
It is 5~80 DEG C.It is re-fed into membrane filtration module after cooling down to regenerative mixed solution, on the one hand pyrosol can be prevented to film mistake
Filter component damages, since temperature is excessively high after the regenerated solvent Returning reacting system that on the other hand also avoidable UF membrane obtains
Reaction system is damaged.Preferably, the cooling temperature before regenerative mixed solution is sent into afterbody membrane filtration module is 5
DEG C, 10 DEG C, 15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C or 80
℃。
Further, using DCS, perhaps PLC is automatically controlled completion or is matched using DCS or PLC film filter regeneration system
Conjunction manually adjusts semi-automatic completion, and the recoil of the membrane filtration module is automatically performed using sequence program.
Compared with the existing technology, have described in the invention in liquid-solid reaction system solid-phase catalyst cleaning and regeneration method
There is following advantage:
The loss of regenerated catalyst can be reduced within 5% by method provided by the invention, the service life of regenerated catalyst
Not less than the 80% of fresh catalyst, regenerative process non-exhaust emission.
Compared with published method of roasting carries out catalyst recovery process, this method is simple and effective, at low cost, economy
Height eliminates loss of the chemicals because of roasting, reduces the loss of catalyst, harmless to environment.
Detailed description of the invention
The attached drawing for constituting a part of the invention is used to provide further understanding of the present invention, schematic reality of the invention
It applies example and its explanation is used to explain the present invention, do not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 is that one kind described in the embodiment of the present invention 1 is cleaned again for solid-phase catalyst in catalyst liquid-solid reaction system
Raw process flow chart；
Fig. 2 is that one kind described in the embodiment of the present invention 2 is cleaned again for solid-phase catalyst in catalyst liquid-solid reaction system
Raw process flow chart；
Fig. 3 is that one kind described in the embodiment of the present invention 3 is cleaned again for solid-phase catalyst in catalyst liquid-solid reaction system
Raw process flow chart.
Description of symbols:
R1- reaction kettle；P1- primary pump；MF1- level-one membrane filtration module；V2- level 2 buffering tank；P2- two stage pump；MF2- bis-
Grade membrane filtration module；；V3- three-level surge tank；P3- triplex；MF3- three-level membrane filtration module；V4- level Four surge tank；P4- tetra-
Grade pump；MF4- level Four membrane filtration module；V5- Pyatyi surge tank；P5- Pyatyi pump；MF5- Pyatyi membrane filtration module；R2- regenerates kettle；
Six grades of P6- pumps；Six grades of membrane filtration modules of MF6-；Seven grades of P7- pumps；1- recirculation heater；2- cooler；3- product post-processes rectifying
System；
Reaction solution of the a- containing catalyst；B1- level-one clear liquid；Dope of the c1- level-one containing catalyst；B2- second level clear liquid；c2-
Dope of the second level containing catalyst；D2- second level mixed solution；B3- three-level clear liquid；Dope of the c3- three-level containing catalyst；D3- three-level
Mixed solution；B4- level Four clear liquid；Dope of the c4- level Four containing catalyst；D4- level Four mixed solution；B5- Pyatyi clear liquid；C5- five
Dope of the grade containing catalyst；D5- Pyatyi mixed solution；Six grades of clear liquids of b6-；E- fresh solvent；F- regenerative mixed solution；G- regeneration
Catalyst.
Specific embodiment
Unless otherwise stated, term used herein all has the meaning that those skilled in the art routinely understand, in order to
It is easy to understand the present invention, some terms used herein have been subjected to following definitions.
It using in the specification and in the claims, singular type "one" and " this " they include plural reference, unless on
Hereafter separately there is clear statement.For example, term " (one) cell " includes the cell of plural number, including its mixture.
All number marks, such as pH, temperature, time, concentration, including range, are all approximations.It is to be understood that although
Term " about " is all added before always not describing all number marks explicitly.While it will also be understood that, although always not clear
Narration, reagent described herein is only example, and equivalent is known in the art.
Below with reference to examples and drawings come the present invention will be described in detail create.
In practical application, the quantum of output of periodic measurement reaction raw materials additional amount and product, byproduct calculates reaction
Conversion ratio yield and selectivity illustrate that catalyst performance is decayed when the selectivity of reaction is gradually reduced.When selective decline
When 10% (can be adjusted according to production needs by owner), it is necessary to carry out catalyst set and wash regeneration.
Reaction system is put into after catalyst regeneration again, repeatedly after regeneration, there can be catalyst inactivation phenomenon.It shows as new
After regenerated catalyst puts into reaction system, selectivity need to just abandon the old catalyst in part still less than design value at this time, supplement equivalent
Fresh catalyst guarantees that reaction system is normally carried out.
Catalyst performance evaluation method is as follows:
Catalyst produces epichlorohydrin reaction for chloropropene, which carries out in stirred tank reactor, catalyst
It is mixed with the abundant fluidised form of reaction raw materials.Reaction condition are as follows: normal pressure, T=50 DEG C of reaction temperature.Chloropropene mass space velocity WHSV (base
In HPECH catalyst)=1.17 h-1.Reaction product uses gas chromatographic analysis.Chloropropene epoxychloropropane catalyst is anti-
Evaluation results are shown in Table 1 in answering.The service life of catalyst in the present invention is defined as: when epoxychloropropane measurement of concetration calculates in product
For the selectivity obtained afterwards lower than 85%), the line duration of catalyst is the service life of catalyst.
Original catalyst dosage is to guarantee catalyst concn 5wt% in slurry-bed reaction kettle, and the service life is about 2000 hours
Left and right.
The evaluation result of 1 catalyst of table during the reaction
The service life of catalyst is about 1848 hours as seen from Table 1, and hereafter selectivity reduces by 10%, falls below 85% or less.
Embodiment 1:
As shown in Figure 1, a kind of for solid-phase catalyst cleaning and regeneration technique in catalyst liquid-solid reaction system, reaction kettle R1
The reaction solution a for including catalyst enters level-one membrane filtration module MF1 from reaction kettle bottom extraction by primary pump P1, through level-one film mistake
The separation that component MF1 realizes catalyst and reaction product is filtered, reaction product is oozed out from membrane tube per-meate side in a manner of clear liquid, obtained
Level-one clear liquid b1 enters product post-processing distillation system 3, and dope c1 of the level-one that film is obtained by filtration containing catalyst is also through circulation pipe
Line largely returns in reaction kettle R1, and concentrated phase c1 of a part containing catalysis is sent into level 2 buffering tank V2.
The recoil cleaning of membrane tube overcomes the pollution of film using the pulse of moment high back voltage in membrane filtration module, is made using methanol
For backflushing medium, transient pulse is carried out to component inner mold tube at regular intervals.Since kickback pressure is higher than the pressure of major cycle,
Backwash liquid quickly penetrates into circulation side from per-meate side, to remove the pollution layer of film surface under the urging of kickback pressure.Recoil time
Interval and recoil time can be adjusted according to the actual situation.Preferably, recoil time is 5~10 seconds.
Level 2 buffering tank V2 receives the c1 of dope containing catalyst and three-level the film filtering from level-one membrane filtration module MF1
The three-level clear liquid b3 of component MF3 exudation, is mixed to get second level mixed solution d2.Second level mixed solution d2 is recycled by two stage pump P2
Into secondary membrane component MF2, the separation of catalyst and reaction product is realized by secondary membrane component MF2, is obtained
Second level clear liquid b2 enters product post-processing distillation system 3, and dope c2 of the second level that film is obtained by filtration containing catalyst is through pipeloop
Most of to return in level 2 buffering tank V2, dope c2 of a part of second level containing catalysis is sent into three-level surge tank V3.
Three-level surge tank V3 receives the c2 of dope containing catalyst and level Four the film filtering from secondary membrane component MF2
The level Four clear liquid b4 of component MF4 exudation, is mixed to get three-level mixed solution d3.Three-level mixed solution d3 is recycled by triplex P3
Into three-level membrane filtration module MF3, the separation of catalyst and reaction product is realized by three-level membrane filtration module MF3, is obtained
Three-level clear liquid b3 enters level 2 buffering tank V2, and dope c3 of the three-level that film is obtained by filtration containing catalyst is largely returned through pipeloop
It returns in three-level surge tank V3, dope c3 of a part of three-level containing catalysis is sent into level Four surge tank V4.
Level Four surge tank V4 receives the c3 of dope containing catalyst and Pyatyi the film filtering from three-level membrane filtration module MF3
The Pyatyi clear liquid b5 of component MF5 exudation, is mixed to get level Four mixed solution d4.Level Four mixed solution d4 is recycled by four-stage pump P4
Into level Four membrane filtration module MF4, the separation of catalyst and reaction product is realized by level Four membrane filtration module MF4, obtains four
Grade clear liquid b4 and level Four the dope c4 containing catalyst, level Four clear liquid b4 enter three-level surge tank V3, dope of the level Four containing catalyst
D4 is largely returned in level Four surge tank V4 through pipeloop, and dope d4 of a part of level Four containing catalysis is sent into Pyatyi surge tank
V5。
Pyatyi surge tank V5 receives level Four dope containing catalyst c4 and six grades of films from level Four membrane filtration module MF4
Six grades of clear liquid b6 of filter assemblies MF6 exudation, are mixed to get Pyatyi mixed solution d5.A part of Pyatyi mixed solution d5 passes through five
Grade pump P5 is recycled into Pyatyi membrane filtration module MF5, and point of catalyst and reaction product is realized by Pyatyi membrane filtration module MF5
From obtaining the dope c5 of Pyatyi clear liquid b5 and Pyatyi containing catalyst, Pyatyi clear liquid b5 enters level Four surge tank V4, and Pyatyi is containing catalysis
The dope c5 of agent is returned in Pyatyi surge tank V5 through pipeloop.A part of Pyatyi mixed solution d5 is sent into regeneration through seven grades of pump P7
Kettle R2.
It regenerates kettle R2 and receives Pyatyi mixed solution d5 and fresh solvent e from Pyatyi surge tank V5, fresh solvent e
For methanol, kettle R2 is regenerated by recirculation heater 1 and maintains 100~200 DEG C of temperature.The regenerative mixed of catalyst and methanol composition is molten
Liquid f a part is pumped into after recirculation heater 1 heats by six grades of pump P6 and returns to regeneration kettle R2, a part regeneration by pipeloop
Mixed solution f is sent into six grades of membrane filtration module MF6 after subcooler 2 is cooled to 5~80 DEG C, by six grades of membrane filtration modules
MF6 realizes the separation of catalysts and solvents, obtains six grades of clear liquid b6 and regenerated catalyst g, six grades of clear liquid b6 enter Pyatyi buffering
Tank V5, regenerated catalyst g Returning reacting system.
Above-mentioned membrane filtration module is ceramic film component, and membrane filtration module at different levels respectively includes 2 membrane filters in parallel.
In membrane filtration processes, catalyst granules stays in ceramic membrane surface and will affect to be filtered again, therefore membrane filter needs periodically recoil, with
The particle of ceramic membrane surface to be rinsed, two membrane filter switchings use, it can prevent that film filtering is caused to be interrupted due to recoil,
To guarantee going on smoothly for cleaning process, recoil time interval is set according to the service condition of film.
Preferably, this cleaning process is used for the catalyst regeneration of liquid phase reactor liquid oxidation process, and it is double to be particularly suitable for liquid
Oxygen water phase closes the catalyst wash regeneration in oxidation reaction.
Cleaning and regeneration is carried out to catalyst using the solid-phase catalyst cleaning and regeneration technique of embodiment 1, regeneration can be urged
The loss of agent is reduced to 5%, and the service life of regenerated catalyst is not less than the 80% of fresh catalyst, and regenerative process is arranged without exhaust gas
It puts.
Technique is washed using this set, can guarantee that the regenerated catalyst service life is not less than 80% (such as evaluation result of fresh catalyst
In 1848 hours * 0.8=1478 hours).
Embodiment 2:
As shown in Fig. 2, a kind of for solid-phase catalyst cleaning and regeneration technique in catalyst liquid-solid reaction system, reaction kettle R1
The reaction solution a for including catalyst enters level-one membrane filtration module MF1 from reaction kettle bottom extraction by primary pump P1, through level-one film mistake
The separation that component MF1 realizes catalyst and reaction product is filtered, reaction product is oozed out from membrane tube per-meate side in a manner of clear liquid, obtained
Level-one clear liquid b1 enters product post-processing distillation system 3, and it is slow that dope c1 of the level-one that film is obtained by filtration containing catalyst is sent into second level
Rush tank V2.
The recoil cleaning of membrane tube overcomes the pollution of film using the pulse of moment high back voltage in membrane filtration module, is made using methanol
For backflushing medium, transient pulse is carried out to component inner mold tube at regular intervals.Since kickback pressure is higher than the pressure of major cycle,
Backwash liquid quickly penetrates into circulation side from per-meate side, to remove the pollution layer of film surface under the urging of kickback pressure.Recoil time
Interval and recoil time can be adjusted according to the actual situation.Preferably, recoil time is 5~10 seconds.
Level 2 buffering tank V2 receives the c1 of dope containing catalyst and three-level the film filtering from level-one membrane filtration module MF1
The three-level clear liquid b3 of component MF3 exudation, is mixed to get second level mixed solution d2.Second level mixed solution d2 is recycled by two stage pump P2
Into secondary membrane component MF2, the separation of catalyst and reaction product is realized by secondary membrane component MF2, is obtained
Second level clear liquid b2 enters product post-processing distillation system 3, and it is slow that dope c2 of the second level that film is obtained by filtration containing catalyst is sent into three-level
Rush tank V3.
Three-level surge tank V3 receives the c2 of dope containing catalyst and level Four the film filtering from secondary membrane component MF2
The level Four clear liquid b4 of component MF4 exudation, is mixed to get three-level mixed solution d3.Three-level mixed solution d3 is recycled by triplex P3
Into three-level membrane filtration module MF3, the separation of catalyst and reaction product is realized by three-level membrane filtration module MF3, is obtained
Three-level clear liquid b3 enters level 2 buffering tank V2, and dope c3 of the three-level that film is obtained by filtration containing catalyst is sent into level Four surge tank V4.
Level Four surge tank V4 receives the c3 of dope containing catalyst and Pyatyi the film filtering from three-level membrane filtration module MF3
The Pyatyi clear liquid b5 of component MF5 exudation, is mixed to get level Four mixed solution d4.Level Four mixed solution d4 is recycled by four-stage pump P4
Into level Four membrane filtration module MF4, the separation of catalyst and reaction product is realized by level Four membrane filtration module MF4, obtains four
Grade clear liquid b4 and level Four the dope c4 containing catalyst, level Four clear liquid b4 enter three-level surge tank V3, dope of the level Four containing catalyst
D4 is sent into Pyatyi surge tank V5.
Pyatyi surge tank V5 receives level Four dope containing catalyst c4 and six grades of films from level Four membrane filtration module MF4
Six grades of clear liquid b6 of filter assemblies MF6 exudation, are mixed to get Pyatyi mixed solution d5.A part of Pyatyi mixed solution d5 passes through five
Grade pump P5 is recycled into Pyatyi membrane filtration module MF5, and point of catalyst and reaction product is realized by Pyatyi membrane filtration module MF5
From obtaining the dope c5 of Pyatyi clear liquid b5 and Pyatyi containing catalyst, Pyatyi clear liquid b5 enters level Four surge tank V4, and Pyatyi is containing catalysis
The dope c5 of agent is returned in Pyatyi surge tank V5 through pipeloop.A part of Pyatyi mixed solution d5 is sent into regeneration through seven grades of pump P7
Kettle R2.
It regenerates kettle R2 and receives Pyatyi mixed solution d5 and fresh solvent e from Pyatyi surge tank V5, fresh solvent e
For methanol, kettle R2 is regenerated by recirculation heater 1 and maintains 100~200 DEG C of temperature.The regenerative mixed of catalyst and methanol composition is molten
Liquid f a part is pumped into after recirculation heater 1 heats by six grades of pump P6 and returns to regeneration kettle R2, a part regeneration by pipeloop
Mixed solution f is sent into six grades of membrane filtration module MF6 after subcooler 2 is cooled to 5~80 DEG C, by six grades of membrane filtration modules
MF6 realizes the separation of catalysts and solvents, obtains six grades of clear liquid b6 and regenerated catalyst g, six grades of clear liquid b6 enter Pyatyi buffering
Tank V5, regenerated catalyst g Returning reacting system.
Above-mentioned membrane filtration module is ceramic film component, and membrane filtration module at different levels respectively includes 2 membrane filters in parallel.
Cleaning and regeneration is carried out to catalyst using the solid-phase catalyst cleaning and regeneration technique of embodiment 1, regeneration can be urged
The loss of agent is reduced to 5%, and the service life of regenerated catalyst is not less than the 80% of fresh catalyst, and regenerative process is arranged without exhaust gas
It puts.
Embodiment 3:
As shown in figure 3, a kind of for solid-phase catalyst cleaning and regeneration technique in catalyst liquid-solid reaction system, reaction kettle R1
The reaction solution a for including catalyst enters level-one membrane filtration module MF1 from reaction kettle bottom extraction by primary pump P1, through level-one film mistake
The separation that component MF1 realizes catalyst and reaction product is filtered, reaction product is oozed out from membrane tube per-meate side in a manner of clear liquid, obtained
Level-one clear liquid b1 enters product post-processing distillation system 3, and dope c1 of the level-one that film is obtained by filtration containing catalyst is also through circulation pipe
Line largely returns in reaction kettle R1, and concentrated phase c1 of a part containing catalysis is sent into level 2 buffering tank V2.
The recoil cleaning of membrane tube overcomes the pollution of film using the pulse of moment high back voltage in membrane filtration module, is made using methanol
For backflushing medium, transient pulse is carried out to component inner mold tube at regular intervals.Since kickback pressure is higher than the pressure of major cycle,
Backwash liquid quickly penetrates into circulation side from per-meate side, to remove the pollution layer of film surface under the urging of kickback pressure.Recoil time
Interval and recoil time can be adjusted according to the actual situation.Preferably, recoil time is 5~10 seconds.
Level 2 buffering tank V2 receives the c1 of dope containing catalyst and three-level the film filtering from level-one membrane filtration module MF1
The three-level clear liquid b3 of component MF3 exudation, is mixed to get second level mixed solution d2.Second level mixed solution d2 is recycled by two stage pump P2
Into secondary membrane component MF2, the separation of catalyst and reaction product is realized by secondary membrane component MF2, is obtained
Second level clear liquid b2 enters reaction kettle R1, and dope c2 of the second level that film is obtained by filtration containing catalyst largely returns to two through pipeloop
In grade surge tank V2, dope c2 of a part of second level containing catalysis is sent into three-level surge tank V3.
Three-level surge tank V3 receives the c2 of dope containing catalyst and level Four the film filtering from secondary membrane component MF2
The level Four clear liquid b4 of component MF4 exudation, is mixed to get three-level mixed solution d3.A part of three-level mixed solution d3 passes through triplex
P3 is recycled into three-level membrane filtration module MF3, and the separation of catalyst and reaction product is realized by three-level membrane filtration module MF3,
Obtained three-level clear liquid b3 enters level 2 buffering tank V2, and dope c3 of the three-level that film is obtained by filtration containing catalyst is returned through pipeloop
It returns in three-level surge tank V3.A part of three-level mixed solution d3 is sent into regeneration kettle R2 by Pyatyi pump P5.
It regenerates kettle R2 and receives three-level mixed solution d3 and fresh solvent e from three-level surge tank V3, fresh solvent e
For methanol, after regenerative mixed solution f a part of catalyst and methanol composition is pumped into the heating of recirculation heater 1 by four-stage pump P4
Regeneration kettle R2 is returned to by pipeloop, regeneration kettle R2 maintains 100~200 DEG C of temperature by recirculation heater 1.A part regeneration
Mixed solution f is sent into level Four membrane filtration module MF4, by level Four membrane filtration module after subcooler 2 is cooled to 5~80 DEG C
MF4 realizes the separation of catalysts and solvents, obtains level Four clear liquid b4 and regenerated catalyst g, and level Four clear liquid b4 enters three-level buffering
Tank V3, regenerated catalyst g Returning reacting system.
Above-mentioned membrane filtration module is ceramic film component, and membrane filtration module at different levels respectively includes 2 membrane filters in parallel.
Cleaning and regeneration is carried out to catalyst using the solid-phase catalyst cleaning and regeneration method of embodiment 3, regeneration can be urged
The loss of agent is reduced to 5%, and the service life of regenerated catalyst is not less than the 80% of fresh catalyst, and regenerative process is arranged without exhaust gas
It puts.
The foregoing is merely the preferred embodiments of the invention, are not intended to limit the invention creation, all at this
Within the spirit and principle of innovation and creation, any modification, equivalent replacement, improvement and so on should be included in the invention
Protection scope within.
Claims (10)
1. one kind is for solid-phase catalyst cleaning and regeneration method in catalyst liquid-solid reaction system, it is characterised in that: this method will
Reaction solution containing inactivation solid catalyst is sent into film filter regeneration system, is washed by being classified set, by solid catalyst surface
Organic matter desorption, realizes catalyst regeneration.
2. one kind according to claim 1 is used for solid-phase catalyst cleaning and regeneration method in catalyst liquid-solid reaction system,
It is characterized by:
Cleaning and regeneration method includes the following steps:
Step 1: the reaction solution containing decaying catalyst enters level-one membrane filtration module from reaction kettle extraction by primary pump, realizes
The separation of catalyst and reaction product obtains reaction product and the dope containing catalyst, after wherein reaction product enters product
Rectification working process is managed, the dope containing catalyst enters level 2 buffering tank；
Step 2: the dope containing catalyst that step 1 obtains enters level 2 buffering tank and mixes with clear liquid, obtained mixed solution warp
It crosses second level and is pumped into secondary membrane component, by the isolated dope and clear liquid containing catalyst of secondary membrane component, clearly
Liquid enters product post-processing rectification working process or returns to reaction kettle；
Step 3: the dope containing catalyst that step 2 obtains enters three-level surge tank and mixes with clear liquid, obtained mixed solution warp
It crosses three-level and is pumped into three-level membrane filtration module, by the isolated dope and clear liquid containing catalyst of three-level membrane filtration module；
Step 4: repeating step 3 until n-1 grades；
The dope containing catalyst that 5:n-1 grades of membrane filtration modules of step are filtered enters n grades of surge tanks and mixes with clear liquid, and what is obtained is mixed
It closes solution a part and is pumped into n grades of membrane filtration modules by n grades, it is isolated containing the dense of catalyst by n grades of membrane filtration modules
Liquid and clear liquid, the isolated dope containing catalyst of n grades of membrane filtration modules returns to n grades of surge tanks, another in n grades of surge tanks
Part mixed solution is pumped into regeneration kettle；
Step 6: being continuously added to fresh solvent in Xiang Zaisheng kettle, and solvent is heated, using fresh solvent to catalyst
Carry out boiling.Regenerative mixed solution is continuously extracted out from regeneration kettle, n+1 grades of membrane filtration modules is sent into through supercooling, by film point
From obtaining clear liquid and regenerated catalyst；
In step 1 to step 6, grade membrane filtration module from three-level membrane filtration module to n+1, membrane filtration modules at different levels are isolated
Clear liquid, which returns, to be mixed in upper level surge tank with the dope containing catalyst.
3. one kind according to claim 2 is used for solid-phase catalyst cleaning and regeneration method in catalyst liquid-solid reaction system,
It is characterized by: dope a part containing catalyst that level-one membrane filtration module to n-1 grades of membrane filtration modules are filtered returns to reaction
Kettle or with level-one surge tank, dope of the another part containing catalyst enters next stage surge tank.
4. one kind according to claim 2 is used for solid-phase catalyst cleaning and regeneration method in catalyst liquid-solid reaction system,
It is characterized by: solid catalyst is by multistage membrane filtration module cleaning, it is 3,4 ,~20 that the set, which washes series n,.
5. one kind according to claim 2 is used for solid-phase catalyst cleaning and regeneration method in catalyst liquid-solid reaction system,
It is characterized by: the membrane filtration module is ceramic film component or other inorganic membrane assemblies.
6. one kind according to claim 2 is used for solid-phase catalyst cleaning and regeneration method in catalyst liquid-solid reaction system,
It is characterized by: the recoil cleaning of the membrane filtration module uses the pulse of moment high back voltage, and it is situated between using methanol as recoil
Matter.
7. one kind according to claim 2 is used for solid-phase catalyst cleaning and regeneration method in catalyst liquid-solid reaction system,
It is characterized by: the fresh solvent selects pure methanol solution.
8. one kind according to claim 2 is used for solid-phase catalyst cleaning and regeneration method in catalyst liquid-solid reaction system,
It is characterized by: regeneration kettle heating temperature is 100~200 DEG C in the step 6.
9. one kind according to claim 2 is used for solid-phase catalyst cleaning and regeneration method in catalyst liquid-solid reaction system,
It is characterized by: in the step 6, regenerative mixed solution be sent into afterbody membrane filtration module before cooling temperature be 5~
80℃。
10. according to claim 1 or 2 a kind of for solid-phase catalyst cleaning and regeneration side in catalyst liquid-solid reaction system
Method, it is characterised in that: perhaps PLC automatically controls completion or cooperates people using DCS or PLC film filter regeneration system using DCS
Work adjusts semi-automatic completion, and the recoil of the membrane filtration module is automatically performed using sequence program.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111001203A (en) * | 2019-12-31 | 2020-04-14 | 河北嘉泰化工科技有限公司 | Plate frame washing device and washing method |
| CN112299953A (en) * | 2020-11-27 | 2021-02-02 | 江苏扬农化工集团有限公司 | Method for treating catalyst regeneration liquid for preparing epichlorohydrin by hydrogen peroxide direct oxidation method |
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| CN102847368A (en) * | 2012-09-07 | 2013-01-02 | 福建锦江石化有限公司 | Method for separating catalyst by using ceramic membrane filter, and apparatus thereof |
| CN110003140A (en) * | 2019-04-26 | 2019-07-12 | 湖南钦宇化工科技有限公司 | The synthesis of epoxychloropropane and the device and method of catalyst on-line regeneration |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102847368A (en) * | 2012-09-07 | 2013-01-02 | 福建锦江石化有限公司 | Method for separating catalyst by using ceramic membrane filter, and apparatus thereof |
| CN110003140A (en) * | 2019-04-26 | 2019-07-12 | 湖南钦宇化工科技有限公司 | The synthesis of epoxychloropropane and the device and method of catalyst on-line regeneration |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111001203A (en) * | 2019-12-31 | 2020-04-14 | 河北嘉泰化工科技有限公司 | Plate frame washing device and washing method |
| CN112299953A (en) * | 2020-11-27 | 2021-02-02 | 江苏扬农化工集团有限公司 | Method for treating catalyst regeneration liquid for preparing epichlorohydrin by hydrogen peroxide direct oxidation method |
| CN112299953B (en) * | 2020-11-27 | 2023-01-10 | 江苏扬农化工集团有限公司 | Method for treating catalyst regeneration liquid for preparing epichlorohydrin by hydrogen peroxide direct oxidation method |
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Application publication date: 20191122 |