A kind of slurry bed reactor catalyst filtration application artTechnical field
The BDO(1 that the present invention is traditional in the past, 4 butyleneglycols) in REPPE method production technique, BYD reactor in ethynylation workshop section, a kind of slurry bed reactor catalyst filtration application system technique and device specifically, butynediol is generated for acetylene and formaldehyde reaction, belong to and relate to Coal Chemical Industry, field of petrochemical industry.
Background technology
Butynediol: English name 2-Butyne-1,4-diol, BYD, Chinese another name Isosorbide-5-Nitrae-butynediol BOZ; 2-butyne-Isosorbide-5-Nitrae-glycol plating luminous agent; Isosorbide-5-Nitrae-butynediol; Isosorbide-5-Nitrae-dihydroxyl-2-butyne; Dihydroxyl 2-butyne; Two methylol acetylene; 2-butyne-1,4-glycol, appearance white or pale yellow crystals white oblique square crystal (being faint yellow after the moisture absorption) Melting_point:58 DEG C Boiling_point 238 DEG C, 145 DEG C of (2kPa) flash_point, 152 DEG C of specific refractory power 1.450 solubleness are water-soluble, acidic solution, ethanol and acetone, be slightly soluble in chloroform, be insoluble to benzene and other character solid butynediol of ether easy deliquescence in 25 c ° air, poisonous, there is the chemical property of binary primary alconol, also can carry out addition reaction.
Butynediol is for organic raw material, solvent, cyanideless electro-plating liquid, also for leatheroid, medicine and pesticide industry, very consequence is occupied in national economy, traditional vapor phase process butynediol production technique is due to the restriction of the factors such as the temperature rise of heat exchange bed and effectiveness factor ofcatalyst, there is synthetic gas per pass conversion low, outlet methanol concentration is low, the shortcoming such as the large and energy expenditure of recycle ratio is large, three-phase slurry bed butynediol synthesis reactor is for object with Air-Water-catalyzer and air-liquid paraffin oil-catalyzer two kinds of systems, have studied hydrodynamics--the Average Air Content of the three-phase slurry bed butynediol synthesis reactor of built-in vertical tube bundle type heat exchanger, bed pressure drop, the critical superficial gas velocity that solid suspends completely, investigate the impact of various factors Fluid Mechanics character, and the Empirical Equation obtained about gas holdup.
Triphase slurry bed reactor is used widely in Chemical Manufacture, as shortening, F-T synthesis etc., the solid particulate normally highly active catalyzer of fine particle lmm in the reactor of three-phase slurry end, can temperature of reaction be controlled equably and remove reaction heat, easily adopt and reach gas in various manners, liquid, Gu the good contact of three-phase, therefore, can in the processing condition comparatively relaxed (as temperature, pressure is under hot condition, the inner filtration device performance adopted is stablized, the solid-liquor separation of continuous slurry bubble stirring tank can be used as, research shows: single still can simulate multi-floating bodies successive processes continuously step by step, the exploitation of this multi-floating bodies process, there is certain practical significance.
Documents: CN200480036825 prepares the method for the determination mixture of THF, BDO and GBL by vapour phase hydrogenation, the production method of current butynediol mainly contains: paraformaldehyde atmospheric solvent process, namely be raw material with paraformaldehyde, solvent is made with ring ethyl ketone etc., under catalyzer acetylene copper exists, in slurry bed reactor, pass into acetylene, after transforming after formaldehyde is complete, stop logical acetylene, then catalyzer is leached, through reaction, concentrated, crystallization both; Acetylene formaldehyde synthesis method, is about to, containing the compressed pressure to 0.4-0.5MPa of acetylene of 80%-90%, be preheated to 70-80 DEG C, deliver to reactor, then can obtain crude product, then through filtering and concentrating, refining both finished product.
Major part for slurry bed reactor is the thin granules of catalyst of paint, painting thin granules of catalyst filtration removal after its reaction process is a problem comparing headache, filter impure, quality product is repeatedly without guarantee, and 2015-2020 China butynediol industry market prospect and investment strategy consultation report in, analyze the market scale of butynediol, butynediol product is for demand status, butynediol race condition and butynediol main enterprises business circumstance, the share of market of butynediol main enterprises, the prediction markets prospect of science is made to the future development of butynediol huge simultaneously.
Summary of the invention
According to the deficiency of foregoing and in the past at traditional BDO(1,4 butyleneglycols) draw in REPPE method production technique: the BYD reactor in ethynylation workshop section, its major function is that acetylene and formaldehyde reaction generate butynediol, and its principal reaction formula is:
CH≡CH + HCHO → CH≡CCH2－OH
CH≡CCH2－OH + HCHO → HO－CH2C≡CCH2－OH
CH≡CH + 2HCHO → HO－CH2C≡CCH2－OH
In this kind of reaction process, in order to improve the yield of speed of response and butynediol, add catalyzer in the reactor, stir with agitator, with fast reaction speed, the candle filter that reaction product is installed by inside reactor, by catalyzer interception in reactor, continue to participate in reaction, clean liquid is able to by candle filter, discharges outside reactor, and through two-stage core type filter process, be purified to after meeting the requirements, remove next step hydrogenation technique, the interception because of catalyzer is completed by the filter cloth on candle filter in essence.
Because filter cloth is textile product, there are some natural intrinsic defect and flaws, the method of sewing of filter bag, the impact of back blowing process, the structure of candle filter, the method of sealing and structure, the material of sealing member, the impact of inefficacy of sealing member etc. many factors, there is the filter cloth of granules of catalyst through candle filter of part, fine filter is entered with the clean liquid of reaction, cause catalyst stream become estranged accurate filter pressure reduction improve, flow velocity declines, accurate filter is forced to the more renew cartridge that frequently stops, the labour intensity of operative employee is caused to increase, unsafe factor increases and production cost significantly improves, basic technical process is as (Fig. 1).
The object of the innovation is: provide a kind of in a lot of chemical technique, in slurry bed reactor, particularly tackle the novel process scheme of catalyzer, tackle the loss of catalyzer, and the catalyzer Returning reactor after interception is continued to use, significantly reduce the consumption of filter element of precision filter, alleviate the labour intensity of workman, reduce over filter and stop the number of times of more renew cartridge and time, increase device security operability.
Former process introduction: the technical process of ethynylation launches round BYD reactor, BYD reactor belongs to slurry bed reactor, whipping appts is provided with bottom it, ensure catalyzer in reactor in suspended state, equipment is built with the candle filter of special construction, for being separated of reaction solution and catalyzer, in working order, formalin slave unit top enters BYD reactor and is full of, acetylene is at service temperature 90oC, under the operating mode of working pressure 0.1MPa, from the acetylene sparger of bottom in access arrangement, bubbling upwards, contact with the surface of formalin at catalyzer, reaction, generate 2-butyne 1, 4 glycol (butynediol).
From the clean liquid of the band catalyzer after candle metre filter, carry out essence filter through accurate filter, filtering precision 1 μm.Clean liquid access acetylene after essence filter steams tower, and unreacted acetylene is discharged through top of tower, by overhead condenser and gas-liquid separator, is circulated back to the import of acetylene compression body, enters BYD reactor again and participate in and react together with fresh acetylene after supercharging.To steam tower clean liquid out from acetylene, enter piptonychia aldehyde tower, the light constituents such as the propiolic alcohol generate unreacted a small amount of formaldehyde and side reaction are steamed by tower top, return BYD ethynylation device, to increase the yield of butynediol together with fresh formaldehyde.
From piptonychia aldehyde tower clean liquid out, enter the 3rd tower weight-removing column, the butynediol aqueous solution of 35% ~ 50% is steamed by tower top, hydrogenation is produced into butyleneglycol, the heavy constituent that the side reaction that tower reactor is discharged generates goes to burn, and in order to prevent the reactions such as butynediol decomposition from occurring, dealdehyder tower and weight-removing column all will under reduced pressure operate, so top of tower is furnished with vapor jet pump, see process flow sheet accompanying drawing 1 accompanying drawing 2.
beneficial effect
The innovation has the following advantages:
Compared with former technique, the catalyzer that reactor leaks down is tackled automatically, and automatically catalyzer is sent back to BYD reactor, stopped catalyzer waste; Equipment can dual-use, and a kind of purposes is automatically tackled by the catalyzer that reactor leaks down; Another kind of function is that in the reactor after catalyst failure, the filtering separation as spent catalyst uses; Technique, compared with former technique, greatly reduces the replacing number of times of filter element of precision filter, reduces production cost, significantly can reduce the labour intensity of operative employee; Can extension reactor machine cycle, reduce system shutdown number of times, improve the effective storage life of equipment, significantly improve economic benefit; Equipment is automatically safe and reliable to operation, is applicable to high temperature, high pressure operating mode, is applicable to the reaction process of inflammable and explosive, poisonous material, and the earth improves device security; Technique dual-use, it is automatic filter, again can after catalyst deactivation, recovery system as spent catalyst uses, special waste catalyst recovery equipment and system need not be gone up again, saved investment, this technological advantage is the device cluster type strainer easy cleaning increased in system, and it is convenient to change.
Accompanying drawing explanation
fig. 1 is new technological flow figure;
fig. 2 is former process flow sheet;
fig. 3 is cluster type strainer schematic diagram;
new technological flow figure illustrates:1 is acetylene compressor; 2 is BYD reactors; 3 is candle filters; 4 is cluster type strainers; 5 is 6-1 μm of fine filters; 7 is formaldehyde pumps; 8,11,12 is overhead condensers; 9,10 is vapor jet pumps; 13,14,15 is gas-liquid separators; 16 is that acetylene steams tower; 17 is piptonychia aldehyde towers; 18 is weight-removing columns; 19,20,21 is reboilers; 22 is backwashing pumps; 23 is residual liquid tanks; The fresh acetylene of A=; The fresh formaldehyde solution of B=; C=clear liquid; D=butynediol; E=make-up catalyst; G=reclaims acetylene.
technical scheme
A kind of slurry bed reactor catalyst filtration application art, it is characterized in that: BYD reactor 2 is arranged on the centre of accurate filter 1, accurate filter 26, a full-automatic cluster type strainer 4 in parallel with straight pipe and valve V1, V2, V3, V4, V5, V6, V7; Backwashing pump 22, residual liquid tank 23, other technical process is constant, only increase a cluster type strainer and associated satellite equipment, original technique can be returned at any time, any impact is not had on former technique, in this technique: " a kind of slurry bed reactor catalyst filtration applied system equipment " also will submit separate case application on the same day.
The granules of catalyst that described cluster type strainer will flow down in BYD ethynylation device, automatically tackle, and automatically returned BYD ethynylation device, avoid catalyst loss, decrease the filter core consumption of lower sequence accurate filter, alleviate the labour intensity of operator, this technique can dual-use, is automatic filter, again can after catalyst deactivation, recovery system as spent catalyst uses, and need not go up special waste catalyst recovery equipment and system again, save investment.
When operating mode 1: when the valve V1 on straight pipe opens, when cluster type strainer terminal valve V2, V3 close, the clean liquid of the reaction in BYD reactor is directly passed through by straight pipe, to reclaiming acetylene tower after accurate filter, identical with former technical process.
When operating mode 2: when straight pipe intervening vaive V1 closes, before and after cluster type strainer, valve V2, V open, and at this moment reaction solution enters cluster type metre filter, clean liquid from cluster type strainer out after, enter accurate filter, accurate filter now only uses as cartridge filter.
In normal conditions, cluster type strainer is fully automatic operation, when the prolongation along with filtration time, cluster type strainer two ends pressure reduction raises, when reaching set(ting)value, device start backwashing pump, valve V7 opens, with filtered clean liquid, to the reverse cleaning of filter element, strainer bottom valve V4 opens simultaneously, liquid returns BYD reactor through pipe connecting together with granules of catalyst, and catalyzer is stayed in BYD reactor and continued to participate in catalytic reaction, after backwash completes, equipment enters formal normal working routine automatically, works on.
When operating mode 3: when catalyzer sufficiently long duration of service in BYD reactor, catalyzer loses activity gradually, when needing to change, at this moment the associated conduit valve open in BYD reactor, 14% ~ 27% catalyzer enters cluster type strainer together with the mixed solution of process liquid, by cluster type strainer spent catalyst and liquid separation, liquid enters residual liquid tank, spent catalyst is intercepted at the outside of filter core, when resistance increases to set(ting)value, blowback program starts automatically, first filter cake is blown down catalyzer from filter core, concentrate in the bottom cone of strainer, when reaching set(ting)value, the residual cake valve V5 of filter bottom opens, waste residue is discharged in the waste catalyst recovery bucket of strainer outside, reclaim.
A kind of slurry bed reactor catalyst filtration applied system equipment, in the middle of BYD reactor and accurate filter, a full-automatic cluster type strainer in parallel with straight pipe and associated satellite equipment, other technical process is constant, original main technique can be kept constant in former BDO ethynylation technique, only increase a cluster type strainer and associated satellite equipment, original technique can be returned at any time, any impact is not had on former technique, it is characterized in that: cluster type strainer 4 is by bundle pipes 4-1, cover 4-2, cylindrical shell 4-3, discharge bucket 4-4, interface 4-5, ear forms 4-6, the many bundle pipes 4-1 of more than one are at least arranged in staving 4-3, bundle pipes 4-1 forms the group of three cover bundle pipes 4-1 in cylindrical shell 4-3, one end opening for feed pipeline section often organized docks with the charging pipe joint 4-2-2 on cover 4-2 and penetrates, the other end often organized connects backflow pipe joint 4-2-21 with circumfluence method.
The force, diameter center both sides of the cover 4-2 of described cluster type strainer 4 is fixed welding two suspension ring base 4-2-1 and three charging pipe joint 4-2-2,5-10cm place welding three backflow pipe joint 4-2-21 under the cylindrical shell mouth of cluster type strainer 4, cluster type strainer 4 cylindrical shell bottom welding funnel-shaped opening 4-4 and welding flange ring interface 4-5, equidistantly on the cylindrical shell top circumferential line of cluster type strainer 4 be welded with four ears 4-6, bundle pipes 4-1 material is silicon carbide ceramic.
The granules of catalyst that new technique and device will flow down in BYD ethynylation device, automatically tackle, and automatically returned BYD ethynylation device, avoid catalyst loss, decrease the filter core consumption of lower sequence accurate filter, alleviate the labour intensity of operator, and saved cost, present invention process dual-use, be automatic filter, again can after catalyst deactivation, the recovery system as spent catalyst uses, special waste catalyst recovery equipment and system need not be gone up again, saved investment.
concrete enforcement
1 contrast be described further with accompanying drawing 2 with reference to the accompanying drawings below, BYD reactor 2 is arranged on the centre of accurate filter 1, accurate filter 26, a full-automatic cluster type strainer 4 in parallel with straight pipe and valve V1, V2, V3, V4, V5, V6, V7; Backwashing pump 22, residual liquid tank 23, other technical process is the same with former technique, constant, only increases a cluster type strainer and associated satellite equipment, valve-off V1, V2, V3, V4, V5, V6, V7; Original technique can be returned at any time, not have any impact to former technique.
When operating mode (1): when the valve V1 on straight pipe opens, cluster type strainer terminal valve V2, when V3 closes, the clean liquid of reaction in BYD reactor is directly passed through by straight pipe, to reclaiming acetylene tower after accurate filter, identical with former technical process, from piptonychia aldehyde tower clean liquid out, enter the 3rd tower weight-removing column, the butynediol aqueous solution of 35% ~ 50% is steamed by tower top, hydrogenation is produced into butyleneglycol, the heavy constituent that the side reaction that tower reactor is discharged generates goes to burn, occur to prevent the reactions such as butynediol decomposition, dealdehyder tower and weight-removing column all will under reduced pressure operate, so top of tower is furnished with vapor jet pump, see process flow sheet accompanying drawing 1 accompanying drawing 2.
Operating mode (2): when straight pipe intervening vaive V1 closes, before and after cluster type strainer, valve V2, V open, and at this moment reaction solution enters cluster type metre filter, clean liquid from cluster type strainer out after, enter accurate filter, accurate filter now only uses as cartridge filter.
In normal conditions, cluster type strainer is fully automatic operation, when the prolongation along with filtration time, cluster type strainer two ends pressure reduction raises, when reaching set(ting)value, device start backwashing pump, valve V7 opens, with filtered clean liquid, to the reverse cleaning of filter element, strainer bottom valve V4 opens simultaneously, liquid returns BYD reactor through pipe connecting together with granules of catalyst, and catalyzer is stayed in BYD reactor and continued to participate in catalytic reaction, after backwash completes, equipment enters formal normal working routine automatically, works on.
Operating mode (3): when catalyzer sufficiently long duration of service in BYD reactor, catalyzer loses activity gradually, when needing to change, at this moment the associated conduit valve open in BYD reactor, 14% ~ 27% catalyzer enters cluster type strainer together with the mixed solution of process liquid, by cluster type strainer spent catalyst and liquid separation, liquid enters residual liquid tank, spent catalyst is intercepted at the outside of filter core, when resistance increases to set(ting)value, blowback program starts automatically, first filter cake is blown down catalyzer from filter core, concentrate in the bottom cone of strainer, when reaching set(ting)value, the residual cake valve V5 of filter bottom opens, waste residue is discharged in the waste catalyst recovery bucket of strainer outside, reclaim.
A kind of slurry bed reactor catalyst filtration applied system equipment, in the middle of BYD reactor and accurate filter, a full-automatic cluster type strainer in parallel with straight pipe and associated satellite equipment, other technical process is constant, in former BDO ethynylation technique, keep original main technique constant, only increase a cluster type strainer and associated satellite equipment, original technique can be returned at any time, any impact is not had on former technique, cluster type strainer 4 is by bundle pipes 4-1, cover 4-2, cylindrical shell 4-3, discharge bucket 4-4, interface 4-5, ear forms 4-6, the many bundle pipes 4-1 of more than one are at least arranged in staving 4-3, bundle pipes 4-1 forms the group of three cover bundle pipes 4-1 in cylindrical shell 4-3, one end opening for feed pipeline section often organized docks with the charging pipe joint 4-2-2 on cover 4-2 and penetrates, the other end often organized connects backflow pipe joint 4-2-21 with circumfluence method.
First on the force, diameter center both sides of the cover 4-2 of cluster type strainer 4, fix welding two suspension ring base 4-2-1, again three charging pipe joint 4-2-2,3 deciles are welded on cover 4-2,5-10cm place welding three backflow pipe joint 4-2-21 under the cylindrical shell mouth of cluster type strainer 4, cluster type strainer 4 cylindrical shell bottom welding funnel-shaped opening 4-4 and welding flange ring interface 4-5, equidistantly on the cylindrical shell top circumferential line of cluster type strainer 4 be welded with four ears 4-6, bundle pipes 4-1 material is silicon carbide ceramic.
Finally just in the cylindrical shell 4-3 of cluster type strainer 4, arrange bundle pipes 4-1 with azygos number, bundle pipes 4-1 forms the group of three cover bundle pipes 4-1 in cylindrical shell 4-3, one end opening for feed pipeline section often organized docks with the charging pipe joint 4-2-2 on cover 4-2 and penetrates, and the other end often organized connects backflow pipe joint 4-2-21 with circumfluence method.
final declaration
More than show and describe principal character of the present invention and advantage, the technician of the industry should understand, the design is not restricted to the described embodiments, the structural principle that part of the present invention is just described described in above-described embodiment and specification sheets, under the prerequisite of spirit and scope not departing from the design, in present invention process: " a kind of slurry bed reactor catalyst filtration applied system equipment " also submits separate case application on the same day, the present invention also will have various changes and modifications, these changes and improvements all should fall within the scope of claimed the design, the claimed scope of the design is by appending claims and equivalent circle thereof.