CN106430228A - Molecular sieve crystallization mother liquor treatment method - Google Patents
Molecular sieve crystallization mother liquor treatment method Download PDFInfo
- Publication number
- CN106430228A CN106430228A CN201610811674.9A CN201610811674A CN106430228A CN 106430228 A CN106430228 A CN 106430228A CN 201610811674 A CN201610811674 A CN 201610811674A CN 106430228 A CN106430228 A CN 106430228A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- mother liquor
- water
- residue
- crystallization mother
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 75
- 238000002425 crystallisation Methods 0.000 title claims abstract description 66
- 230000008025 crystallization Effects 0.000 title claims abstract description 66
- 239000012452 mother liquor Substances 0.000 title claims abstract description 60
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 150000001412 amines Chemical class 0.000 claims abstract description 35
- 230000018044 dehydration Effects 0.000 claims abstract description 27
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 239000010413 mother solution Substances 0.000 claims description 29
- 230000006837 decompression Effects 0.000 claims description 28
- 230000008569 process Effects 0.000 claims description 21
- 238000007599 discharging Methods 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 19
- 238000010521 absorption reaction Methods 0.000 claims description 18
- 239000012530 fluid Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 238000001704 evaporation Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- 238000010129 solution processing Methods 0.000 claims description 13
- 230000008020 evaporation Effects 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000002699 waste material Substances 0.000 claims description 8
- 238000004939 coking Methods 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 159000000013 aluminium salts Chemical class 0.000 claims description 3
- 238000013461 design Methods 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 238000007790 scraping Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 3
- 241000269350 Anura Species 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000003818 cinder Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 238000010079 rubber tapping Methods 0.000 claims description 2
- 230000009183 running Effects 0.000 claims description 2
- 241000894007 species Species 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 238000009833 condensation Methods 0.000 abstract description 3
- 230000005494 condensation Effects 0.000 abstract description 3
- 239000000571 coke Substances 0.000 abstract 1
- 238000001291 vacuum drying Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 238000009434 installation Methods 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000001471 micro-filtration Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- -1 ethylene, propylene Chemical group 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005360 mashing Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- GHTGICGKYCGOSY-UHFFFAOYSA-K aluminum silicon(4+) phosphate Chemical compound [Al+3].P(=O)([O-])([O-])[O-].[Si+4] GHTGICGKYCGOSY-UHFFFAOYSA-K 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011026 diafiltration Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 238000009432 framing Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/02—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in boilers or stills
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/42—Regulation; Control
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
The invention relates to a molecular sieve crystallization mother liquor treatment method, which mainly solves the problems that in the prior art residues of crystallization mother liquor after water and organic amine are removed from the molecular sieve crystallization mother liquor are easy to precipitate and coke and difficult to discharge. The molecular sieve crystallization mother liquor treatment method is adopted and comprises the steps of performing reduced pressure dehydration, condensation liquid rectification and vacuum drying, recovering organic amine and the like, the problems are well solved, and the method can be applied to molecular sieve crystallization mother liquor treatment.
Description
Technical field
The present invention relates to a kind of molecular sieve mother solution processing method, the especially process of SAPO-34 molecular sieve mother solution
Method.
Background technology
Methanol-to-olefins (Methanol-To-Olefin, abbreviation MTO) refer to what utilization was generally produced by natural gas or coal
Methanol, generates the Technology of the low-carbon alkenes such as polymer grade ethylene, propylene under catalyst action.MTO technology has been opened up from non-
Petroleum resources set out and produce a new technology route of petroleum chemicals, it has also become new forms of energy resource technical research exploitation focus it
One.According to China's national situation, the MTO technology with coal or natural gas as raw material for the development, can effectively improve China's oil shortage of resources,
Rely heavily on the present situation of crude oil import.
With the lasting research to MTO catalyst, 1984, UCC developed SAPO-n Series Molecules sieve.SAPO- now
34 optimum catalysts being acknowledged as MTO.SAPO-34 has elliposoidal cage and the three-dimensional open-framework that 8 yuan of rings are constituted, aperture
A diameter of 0.43～0.50nm.This molecular sieve there is less aperture structure, moderate acid and good hydrothermal stability.
SAPO-34 Zeolite synthesis method has been carried out industrialized only hydrothermal synthesis method, and synthesis technique is plastic crystallization, crosses diafiltration
Wash, three processes of powder are beaten in drying.The filtrate that crystallization slurry obtains through filtration separation is referred to as crystallization mother liquor, can not in crystallization mother liquor
Avoid containing unreacting material such as phosphorus sial salt, template agent and primary structure unitses, secondary structure unit, rudimentary skeleton knot
The colloid of the formation such as structure or float, as produced by by Zeolite synthesis, crystallization mother liquor directly discharges, and float and COD etc. are no
Method reaches discharging standards, when carrying out harmless treatment to crystallization mother liquor, because such colloid and float cannot adopt poly- third
Acrylamide flocculating sedimentation, has a strong impact on crystallization mother liquor handling process and implements.Luan Guoyan etc. propose in crystallization mother liquor add sun from
Sub- polyacrylamide and calcium chloride combination flocculant dephosphorization, Phosphorus From Wastewater reaches far away sewage drainage standard.Zou Lingfeng using to
Add aluminum sulfate sedimentation silicon in crystallization mother liquor, reduce outer draining concentration of suspension, also fail thoroughly to solve the environment of such waste liquid
Pollution problem.CN1116099C, CN1205987A propose to use microfiltration film process crystallization mother liquor, but adopt the method, microfiltration fenestra
In crystallization mother liquor when footpath is big, colloid and float can not remove completely, colloid and float in microfiltration membrane aperture hour crystallization mother liquor
Blocking microporous can cannot filter, and partial organic substances dissolving cannot be carried out with micro-filtration membrane separating in a solvent.
The research that crystallization mother liquor is processed more concentrates on and crystallization mother liquor circulates the synthesis being used for molecular sieve.
CN101935050B propose using crystallization mother liquor synthesized silicon-aluminum phosphate molecular sieve method, CN102190312A propose by ZSM-5,
In the method preparing various molecular sieves, CN1194943 A carries TS-1, MCM-22 or Beta equimolecular sieve crystallization mother liquor fully recovering
Go out the method synthesizing ZSM-5 molecular sieve with NaY molecular sieve crystallization mother liquor, CN102249257 A proposes in the production of SUZ-4 molecular sieve
Crystallization mother liquor circulates for producing SUZ-4 molecular sieve methods.Other as CN101121522A, CN103172083A,
CN102050468A etc. proposes for crystallization mother liquor or dried powder body to be used for Zeolite synthesis dispensing.Crystallization mother liquor recycles
Mainly have two kinds of forms, a kind of be mother solution indirect utilization technology, that is, a kind of synthesis mother liquid of molecular sieve pass through to process or do not locate
Reason, for synthesizing other molecular sieves or preparing other compounds, reaches and reduces environment dirt using effectively composition in molecular sieve mother solution
The technology of dye.Indirect utilization technology need not generate same molecular sieve, there is not mother liquid recycling, can be not required to examine
Consider the accumulation problem of mother solution intermediate ion, but the indirect utilization technology of mother solution also faces the application problem of new synthetic product.Also have one
Planting is the direct reuse technology of crystallization mother liquor, through processing all or part that is even left intact after that is, crystallization mother liquor is collected
Mother solution is directly used in the synthesis of same molecules sieve.Mother solution to be realized does not process direct reuse, condition very harsh it is necessary to meet
The total amount of mother solution too big, mother solution reuse amount can not can not affect the charge ratio that circulates in synthesis and keep in recycling
In mother solution when balance, recycling, the concentration of various ions keeps relative equilibrium, does not contain the influence factor producing stray crystal in mother solution.
Crystallization mother liquor after treatment or directly as raw materials for production be back to system with molecular sieve for preparing for when, because of mother solution and dried
Have containing unreacting material, primary structure unitses, secondary structure unit, rudimentary framing structure, cationic low molecule in powder body
Machine electrolyte etc., can affect zeolite product quality repeatedly during reuse, the molecular sieve using crystallization mother liquor reuse synthesis is prepared into
Catalyst performance how, seldom reports in patent.Document, patent report utilization crystallization mother liquor synthesis of molecular sieve technology a lot,
But apply to the few of industrial installation, also a lot of technical problems need to solve, and molecular sieve industrial installation is true
Just accomplishing the little of crystallization mother liquor zero-emission, major part is still as discharge of wastewater.SAPO-34 molecular sieve water heat synthetic system is multiple
Miscellaneous, synthesis difficulty is big, and the technology of current SAPO-34 crystallization mother liquor reuse synthesis of molecular sieve have not been reported, and its crystallization mother liquor needs
Will after treatment could qualified discharge, but process again extremely difficult.We once process SAPO-34 using traditional rectification mode and divide
Son sieve crystallization mother liquor, through distillation, from recovered overhead, tower reactor obtains a small amount of siliceous phosphorus to mother solution for the organic amine of the overwhelming majority and water
The waste residue of aluminium salt, is further processed into solid waste.But the greatest problem encountered is as the evaporation of organic amine, mother solution gradually becomes glutinous
Retrogradation and precipitate, even coking, cause distillation column bottom of towe, filler blocking, rectification efficiency constantly declines, and tower bottoms discharging is stranded
Difficulty, distillation operation cannot stable operation.We can also carry out the process of crystallization mother liquor using the method being spray-dried, and obtains powder
Shape solid.But solid content is less than to 10% liquid, directly utilizes spray dried form energy consumption very big, uneconomical, and spray
Mist be dried using hot-air be thermophore, although the organic amine of evaporation can carry out after mixing with air with moisture condense recovery molten
Agent, but because air capacity is too big, the response rate is not high, and in tail gas organic amine content to reach qualified discharge highly difficult, have simultaneously
A little aerial explosion limits of organic amine such as triethylamine are very low, and safety there is also problem, so, SAPO-34 molecular sieve is brilliant
Changing mother liquid disposal has become one of process of industrialization difficult problem, finds process SAPO-34 molecule on a kind of industrial installation
The method of sieve crystallization mother liquor has very big realistic meaning.
The present invention targetedly solves this problem.
Content of the invention
The technical problem to be solved is the residue that in prior art, crystallization mother liquor removes after moisture content and organic amine
Easily precipitation coking, be difficult the problem of discharging, a kind of new molecular sieve mother solution processing method is provided.The method is used for molecular sieve
During crystallization mother liquor is processed, have the advantages that the residue after crystallization mother liquor removing moisture content and organic amine is difficult to precipitate coking, easy discharging.
For solving the above problems, the technical solution used in the present invention is as follows：A kind of molecular sieve mother solution processing method, bag
Include following steps：
1) crystallization mother liquor self-priming enters the distillating still being pumped in the decompression dehydration device of negative pressure by vacuum pump A, and feed liquor terminates
After be passed through steam, in chuck, distillating still is heated, makes the organic amine in crystallization mother liquor and water evaporates, from crystallization mother liquor
In the organic amine that steams and vapor enter condenser, condensed fluid enters solvent tank；Agitating device is set in distillating still, steams
In tank body during evaporating, blender rotates, and drives stirring paddle to rotate, makes to be evaporated material and constantly stir, to keep distilling feed liquid
It is heated evenly, be also prevented from residue simultaneously and coking is formed on tank body cavity wall；
2) after in distillating still, residue moisture content reaches requirement, distillation terminates, automatically into tapping process；Stir during deslagging
Axle is automatically changed to rotate forward, and by the scraping blade that helical form is arranged, residue is from inside to outside released, and drains down into waste residue from slag-drip opening
Pulp storing tank；
3) close slag-discharging valve after deslagging terminates, enter next batch processing, during decompression dehydration, every kettle is that interval is grasped
Make, for realizing follow-up dry run continuous operation, using two or more decompression dehydration equipment parallel runnings；
4) residue in waste residue pulp storing tank is delivered to by slurry delivery pump and is dried process, by pressure nozzle,
Make residue be evenly distributed on to be dried on dry zone；Vacuum belt drier adopts the negative-pressure operation that vacuum pump B evacuation is formed, residual
Slag, through drying, after reaching the water content of requirement, forms solid dry powder discharging；
5), when residue is dried in vacuum belt drier, in vacuum belt drier, the organic amine of evaporation and vapor enter
Enter condenser, condensed fluid enters described solvent tank and collects, the condensed fluid in solvent tank enter rectifying column carry out organic amine and
The separation of water, the organic amine isolated and water circulation reuse；
6) gas of described vacuum pump A, vacuum pump B outlet is introduced absorption tower, by circulation fluid spray-absorption gas
Organic amine after high altitude discharge.
In technique scheme, after crystallization mother liquor refers to crystallization synthetic reaction, crystallization slurry removes molecule through filtration separation
Sieve the filtrate obtaining, can be the crystallization mother liquor of each molecular sieve analog, preferably SAPO molecular sieve, most preferably hydrothermal synthesis method is formed
SAPO-34 molecular sieve.
In technique scheme, in crystallization mother liquor, comprise silicon, phosphorus, aluminium salt, comprise or do not contain template agent, template agent is to have
Machine amine, crystallization mother liquor solid content is generally 3-10%.
In technique scheme, the temperature in described decompression dehydration device distillating still is 30-100 DEG C, preferably 40-60 DEG C；
Pressure is -0.03～-0.01Mpa, preferably -0.085～-0.099Mpa
In technique scheme, the preferred water ring vacuum pump of decompression dehydration device intermediate pump, the recirculated water used by vacuum pump
Preferably employ decompression dehydration device evaporation condensate, it is possible to reduce the consumption of water.
In technique scheme, according to the organic amine component containing in template agent, rectifying column can be one or more.
In technique scheme, different according to the species of template agent, different using circulating absorption solution in absorption tower, Ke Yishi
Acid water or alkaline water, preferably pure water.
In technique scheme, key technology is exactly to be mounted with rabbling mechanism in the alembic of decompression dehydration device, should
Rabbling mechanism makes to be evaporated material and constantly mixes, stirs, and on the one hand enhances heat-transfer effect, on the other hand makes material be difficult to stick
Wall.During stirring, blender can voluntarily main story and reversion.At the end of evaporation, material can be released alembic by screw mixing oar.
In technique scheme, decompression dehydration device residue moisture control is very crucial, and water content is too low, residue viscosity
Greatly, poor fluidity, not only discharging is difficult, and it is difficult to be likely to result in cloth when residue enters vacuum belt-type dryer.Decompression is de-
Water installations letting cinder control, can be controlled by vapo(u)rizing temperature in tank body, start when temperature of charge reaches design temperature to arrange
Slag it is also possible to be controlled by condensed fluid load, when the amount that condensed fluid reaches requirement starts deslagging.Preferably by condensed fluid
Amount controls the deslagging time.Residue moisture content is 30-80%, preferably 45-55%.
In technique scheme, decompression dehydration device discharges residue, be further dried can using spray drying process or
Person's expansion drying method, it would however also be possible to employ vacuum belt type drying method.Due to reaching 50% about containing solvent in residue, and also
Containing organic amine substance, this kind of solvent must reclaim, drying process with atomizing or expansion drying technique air as heat carrier,
And air consumption is big, the difficult solvent recovery of evaporation, and be spray-dried energy consumption and be more than vacuum belt type drying technique, some are organic
The aerial explosion limit of amine (as triethylamine) is very low, and safety there is also problem, it is preferred, therefore, that vacuum belt type drying technique
Drying meanss as slurry residues.
In technique scheme, described vacuum belt-type dryer is continuous feed, continuous discharge.Permissible in Dewar vessel
Design arrangement 2-15 layer dry zone, by continuous slurry feeder and distributing device, material thin uniform layer cloth is placed on dry zone,
Increased material contact area, drying efficiency is high, drying residencing time is 20-90min.
In technique scheme, described vacuum belt-type dryer operating pressure is -0.03～-0.01Mpa, preferably -0.085
～-0.099Mpa.Vacuum needed for operation, can be provided by conventional vacuum pump.Preferably water ring+Roots vacuum system, Neng Gouti
Separate the recycle-water obtaining for the recirculated water needed for higher vacuum, water ring pump using rectifying column.Using a period of time, organic
When amine content is higher, then send rectifying column to process, which reduce the consumption of recirculated water.
In technique scheme, described vacuum belt-type dryer drives dry zone to set by the special rubber roll of Motor drive
Speed move along drying machine cylinder direction, every dry zone following be designed with the separate heating plate of multistage and one cold
But plate, dry zone is fitted tightly with heating plate, coldplate, by the energy transmission required for being dried to thing in the way of transmission of heat by contact
Material.Heater plate mode can be hot water, electricity, conduction oil or steam, and temperature is 60 DEG C -200 DEG C, preferably 130 DEG C -160 DEG C.
Cooling section temperature 30-60 DEG C.
In technique scheme, the dried material of described vacuum belt-type dryer can block discharging or powdery discharging, excellent
Select powdery discharging, pulverize under vacuum, it is to avoid dust from flying, realized by vacuum continuous discharge device and vacuum collecting machine
Continuous discharge.Solid dry powder moisture content is less than 2%.
In technique scheme, described vacuum belt-type dryer drying has solvent recovery unit.Slurry residues when being dried,
The organic amine of evaporation and vapor enter condenser condensation, and condensed fluid is collected automatically into condensate tank.Vacuum pump is discharged
Gas, enters absorption tower, absorbs Organic substance, clean gas high altitude discharge further, so thoroughly solves environmental issue.
In this patent, crystallization mother liquor self-priming enters the decompression dehydration device being pumped into negative pressure, and feed liquor terminates rear steam pressure-reducing
Valve automatically opens up and is passed through steam, in chuck, alembic is heated, and makes the organic amine in crystallization mother liquor and water evaporates.Brilliant
Change mother solution complicated components, be evaporated to the later stage, when moisture is low, if heating-up temperature is high, easily causes material coking and black, stickiness
Increasing, poor fluidity, so the present invention adopts operating under vacuum, reducing evaporating temperature.Key technology of the present invention is de- in decompression
Setting agitating device in water installations, in tank body in still-process, blender rotates, and drives stirring paddle automatically to rotate forward reversion, makes to be steamed
Stimulating food material constantly stirs, and to keep distilling being heated evenly of feed liquid, is also prevented from residue simultaneously and forms coking in tank body cavity wall.
Solid dry powder is mainly silicon phosphorus aluminium salt inorganic matters, send qualified solid waste unit to process further.
Organic amine in crystallization mother liquor described in this patent and water all obtains reuse it is achieved that non-wastewater discharge purpose, both
Take full advantage of resource, protect environment again.The waste gas that crystallization mother liquor produces in processing procedure all realizes qualified discharge, brilliant
The solid powder obtaining after changing mother liquid disposal can reach the requirement of general fixed-end forces.All locate in crystallization mother liquor whole process processing procedure
Operate in closing, under vacuum state, it is to avoid the risk of hazardous materials spillage, and whole realize automatically, continuous operation, work
Intensity substantially reduces, and is a kind of economy, environmental protection, the method being easy to commercial Application.This inventive technique thoroughly solves molecular sieve row
A difficult problem for industry crystallization mother liquor difficult treatment, achieves preferable technique effect.
Brief description
Fig. 1 is the schematic flow sheet of the method for the invention.
, by decompression dehydration device 2 evacuation, after vacuum reaches to a certain degree, crystallization mother liquor is from mother liquor holding tank 1 for vacuum pump 6
Suck decompression dehydration device 2, feed liquor is heated after terminating, the steam being evaporated enters condenser 4, condense and form liquid,
Automatically into solvent tank 7, solvent is continuously added to rectifying column 14 through feed pump 11 to carry out separately obtaining water (tower base stream condensed fluid
18) and organic amine (overhead stream 16) is separately recovered utilization.Vacuum pump 6 expellant gas enter absorption tower 13, through pipe after absorption
Line 15 high altitude discharge.After distillation terminates, waste residue slurry enters pulp storing tank 3, adds vacuum belt drier 8 through mashing pump 5.Very
Empty pump 10 carries out evacuation to vacuum belt drier 8.Slurry is dried on the dry zone of vacuum belt drier 8, steams
After the condensed device of solvent 9 condensation sent out, enter solvent tank 7.Vacuum pump 10 expellant gas enter absorption tower 13 and absorb.It is dried
Solid material afterwards is after vacuum disintegrating machine 12 pulverizing from discharging opening 17 discharging.
Below by embodiment, the invention will be further elaborated, but is not limited only to the present embodiment.
Specific embodiment
【Embodiment 1】
Using the flow process shown in Fig. 1.Crystallization mother liquor used is to obtain through filtration separation after SAPO-34 Zeolite synthesis
Filtrate, template agent triethylamine content is 7.6%, and mother solution total solid content is about 9%；Test decompression dehydration device, alembic holds
Long-pending 500L, jacket steam heats, and operating temperature is 39 DEG C.
When bringing into operation, vacuum pump, by decompression dehydration apparatus system evacuation, reaches liquid feed valve after -0.091MPa after vacuum
Door automatically opens up feed liquor, liquid inlet volume 250L/ time；Feed liquor is heated with steam after terminating, and steam pressure 0.17MPa opens simultaneously
Blender in dynamic tank body.
Mother liquid evaporation steam out enters shell and tube condenser after aerosol cleaner unit simple filtration, condenses and forms liquid
Body, condensed fluid, automatically into wastewater storage tank, collects a certain amount of rear entrance rectifying column, according to the boiling point containing component in organic amine wastewater
The different distillation and separation methods using routine, water is separated with organic amine, and purity is more than 98%, all returns crystallization process and reclaims
Using.
The gas of vacuum pumped enters absorption tower, absorption tower diameter of phi 1600mm, tower height 10m, built-in tinsel network planning
Whole filler, carries out spray washing absorption with pure water, and in the tail gas after absorption, organic amine content is less than 0.1mg/m3, major part is almost
Can't detect, can be with qualified discharge.
After the solvent of evaporation reaches 220L, stop heating, total evaporation time is 107min.Open slag-discharging valve, lead to
The scraping blade crossing helical form setting is from inside to outside released residue, and discharges downwards from slag-drip opening, enters pulp storing tank.Result of the test
Obtain residue 25.3kg, water content is 50-51%.Decompression dehydration device deslagging terminates exhaust casing and closes, and decompression dehydration device enters
Enter next batch processing.
Test vacuum belt drier, heat exchange area 10, wherein heating surface (area) (HS 9, if two thermals treatment zone, one is cold
But area, film-cooled heat 1, two-layer dry zone altogether, using conduction oil circulating-heating, the dry materials time of staying is 70min.Vacuum
Unit is water ring+Roots's unit.
Vacuum belt drier system evacuation reaches -0.099MPa, the pulp-like waste residue that decompression dehydration device is discharged
Vacuum belt drier is continuously added to by mashing pump, so that material is evenly distributed on dry zone through drive nozzle, inlet amount
30kg/h.Set heating-up temperature：First 140 DEG C of area, 140 DEG C of the secondth area, 40 DEG C of the 3rd area.Residue enters vacuum belt drier
Enter heated zones afterwards to be dried, cooled down in cooling zone, continuously gone out by vacuum continuous discharge device and vacuum collecting machine
Material, load is about 15kg/h.Solid powder moisture content is 0.73%.
【Embodiment 2】
According to the condition described in embodiment 1 and step, decompression dehydration device obtains the residue that water content is 50-51%, enters
Enter vacuum belt drier system to be dried, only change Heating Zone Temperature：First 130 DEG C of area, 100 DEG C of the secondth area, the 3rd area
40 DEG C, other conditions are with embodiment 1.Obtaining discharging solid powder moisture content is 1.57%.
【Embodiment 3】
According to the condition described in embodiment 1 and step, decompression dehydration device obtains the residue that water content is 50-51%, enters
Enter vacuum belt drier system to be dried, only change heating-up temperature：First 160 DEG C of area, 160 DEG C of the secondth area, the 3rd area 40
DEG C, other conditions are with embodiment 1.Obtaining discharging solid powder moisture content is 0.38%.
Claims (9)
1. a kind of molecular sieve mother solution processing method, comprises the steps：
1) crystallization mother liquor self-priming enters the distillating still being pumped in the decompression dehydration device of negative pressure by vacuum pump A, and feed liquor is logical after terminating
Enter steam, in chuck, distillating still is heated, make the organic amine in crystallization mother liquor and water evaporates, steam from crystallization mother liquor
The organic amine going out and vapor enter condenser, and condensed fluid enters solvent tank；Agitating device is set in distillating still, distilled
In tank body in journey, blender rotates, and drives stirring paddle to rotate, makes to be evaporated material and constantly stir, to keep distilling being heated of feed liquid
Uniformly, it is also prevented from residue simultaneously and coking is formed on tank body cavity wall；
2) after in distillating still, residue moisture content reaches requirement, distillation terminates, automatically into tapping process；During deslagging shaft from
Move and be changed to rotate forward, by the scraping blade that helical form is arranged, residue is from inside to outside released, and drain down into waste residue slurry from slag-drip opening
Storage tank；
3) close slag-discharging valve after deslagging terminates, enter next batch processing, during decompression dehydration, every kettle is intermittently operated, is
Realize follow-up dry run continuous operation, using two or more decompression dehydration equipment parallel runnings；
4) residue in waste residue pulp storing tank is delivered to by slurry delivery pump and is dried process, by pressure nozzle, makes residual
Slag is evenly distributed on and is dried on dry zone；Vacuum belt drier adopts the negative-pressure operation that vacuum pump B evacuation is formed, residue warp
Cross dry, after reaching the water content of requirement, form solid dry powder discharging；
5), when residue is dried in vacuum belt drier, in vacuum belt drier, the organic amine of evaporation and vapor entrance are cold
Condenser, condensed fluid enters described solvent tank and collects, and the condensed fluid in solvent tank enters rectifying column and carries out organic amine and water
Separation, the organic amine isolated and water circulation reuse；
6) gas of described vacuum pump A, vacuum pump B outlet is introduced absorption tower, by having in circulation fluid spray-absorption gas
High altitude discharge after machine amine.
2. according to claim 1 molecular sieve mother solution processing method it is characterised in that described crystallization mother liquor be crystallization close
After becoming reaction, crystallization slurry removes, through filtration separation, the filtrate that molecular sieve obtains；Silicon, phosphorus, aluminium salt is comprised, bag in crystallization mother liquor
With or without template agent, template agent is organic amine, and crystallization mother liquor solid content is 3-10%, and molecular sieve is SAPO series.
3. according to claim 2 molecular sieve mother solution processing method it is characterised in that described molecular sieve be SAPO-34.
4. according to claim 1 molecular sieve mother solution processing method it is characterised in that described decompression dehydration device distillation
Temperature in kettle is 30-100 DEG C, and pressure is -0.03～-0.01Mpa；According to the organic amine component species containing in template,
Rectifying column quantity is at least one, different using circulating absorption solution in absorption tower, selected from acid water or alkaline water；Described vacuum belt
The dried material of formula exsiccator can block discharging or powdery discharging, described solid dry powder moisture content is less than 2%.
5. according to claim 4 molecular sieve mother solution processing method it is characterised in that described decompression dehydration device distillation
Temperature in kettle is 40-60 DEG C, and pressure is -0.085～-0.099Mpa；The use of circulating absorption solution is pure water in described absorption tower.
6. according to claim 1 molecular sieve mother solution processing method it is characterised in that described vacuum pump A be Water-ring vacuum
Pump, the recirculated water used by vacuum pump adopts the evaporation condensate in decompression dehydration device；Vacuum pump B is water ring+Roots vacuum machine
Group, the recirculated water needed for water ring pump separates, using rectifying column, the recycle-water obtaining；Decompression dehydration device letting cinder control, can pass through
In tank body, vapo(u)rizing temperature is controlled, and starts deslagging when temperature of charge reaches design temperature it is also possible to pass through condensed fluid discharging
Amount is controlled, when the amount that condensed fluid reaches requirement starts deslagging；After in distillating still, residue moisture content reaches 30-80%, steam
Evaporate end.
7. according to claim 6 molecular sieve mother solution processing method it is characterised in that using condensing liquid quantity control deslagging
Time；After in distillating still, residue moisture content reaches 45-55%, distillation terminates.
8. according to claim 1 molecular sieve mother solution processing method it is characterised in that described vacuum belt-type dryer is
Continuous feed, continuous discharge, arrange 2-15 layer dry zone in Dewar vessel, by continuous slurry feeder and distributing device, will
Material thin uniform layer cloth is placed on dry zone, drying residencing time be 20-90min, vacuum belt-type dryer operating pressure be-
0.03～-0.01Mpa；Described vacuum belt-type dryer drives the speed edge to set for the dry zone by the special rubber roll of Motor drive
Move in drying machine cylinder direction, the following of every dry zone is designed with the separate heating plate of multistage and a coldplate, does
Dry band is fitted tightly with heating plate, coldplate, by the energy transmission required for being dried to material in the way of transmission of heat by contact.Heating
Plate mode of heating is hot water, electricity, conduction oil or steam, and temperature is 60 DEG C -200 DEG C, and cooling section temperature is 30-60 DEG C.
9. according to claim 8 molecular sieve mother solution processing method it is characterised in that described vacuum belt-type dryer behaviour
Making pressure is -0.085～-0.099Mpa；In vacuum belt-type dryer, heating-up temperature is 130 DEG C -160 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610811674.9A CN106430228B (en) | 2016-09-08 | 2016-09-08 | Molecular sieve mother solution processing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610811674.9A CN106430228B (en) | 2016-09-08 | 2016-09-08 | Molecular sieve mother solution processing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106430228A true CN106430228A (en) | 2017-02-22 |
| CN106430228B CN106430228B (en) | 2018-09-21 |
Family
ID=58165481
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610811674.9A Active CN106430228B (en) | 2016-09-08 | 2016-09-08 | Molecular sieve mother solution processing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106430228B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108569703A (en) * | 2017-03-10 | 2018-09-25 | 临沂大学 | A method of recycling mother liquor synthesizing Si-Al phosphorus molecular sieve |
| CN108569704A (en) * | 2017-03-10 | 2018-09-25 | 临沂大学 | A kind of Zeolite synthesis equipment |
| CN108569706A (en) * | 2017-03-10 | 2018-09-25 | 临沂大学 | A method of recycling mother liquor synthesizing Si-Al molecular sieve |
| CN109081362A (en) * | 2017-06-13 | 2018-12-25 | 神华集团有限责任公司 | The recovery method of remaining template during system with molecular sieve for preparing is standby |
| CN109305690A (en) * | 2018-10-17 | 2019-02-05 | 山东齐鲁华信高科有限公司 | Utilize the green synthesis method of recycling template and crystallization mother liquor synthesizing P-Al si molecular sieves |
| CN114433250A (en) * | 2020-10-16 | 2022-05-06 | 中国石油化工股份有限公司 | Slurry recovery device, slurry preparation system and slurry recovery method |
| CN114516644A (en) * | 2020-11-19 | 2022-05-20 | 中国石油化工股份有限公司 | Drying and crushing method of SAPO-34 molecular sieve |
| CN117582731A (en) * | 2024-01-18 | 2024-02-23 | 宿迁南翔化学品制造有限公司 | Multistage condensing distillation mechanism for large-scale malonic acid production |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225772A (en) * | 2011-04-15 | 2011-10-26 | 大连理工大学 | Method for utilizing molecular sieve systhesis mother liquor |
| CN102491364A (en) * | 2011-12-01 | 2012-06-13 | 上海绿强新材料有限公司 | Method and device for recycling lithium from exchange waste fluid containing lithium |
| CN102502687A (en) * | 2011-10-18 | 2012-06-20 | 大连理工大学 | Method for greenly synthesizing Ti-Si molecular sieve |
| CN103723742A (en) * | 2013-12-31 | 2014-04-16 | 中国天辰工程有限公司 | Post-treatment method for washing, drying and calcining SAPO (silicoaluminophosphate) molecular sieve |
| CN203820665U (en) * | 2014-04-28 | 2014-09-10 | 中节能清洁技术发展有限公司 | Distilling recovery system for dimethylformamide rectification raffinate |
| CN104743566A (en) * | 2013-12-26 | 2015-07-01 | 中国石油化工股份有限公司 | Method for recovering free template in molecular sieve slurry or filtrated stock |
| CN105198147A (en) * | 2015-09-15 | 2015-12-30 | 博天环境集团股份有限公司 | Treatment method for organic amine waste water generated by producing molecular sieve and carrier catalyst thereof |
| CN105314757A (en) * | 2014-07-03 | 2016-02-10 | 中国石油化工股份有限公司 | Treatment method of mother liquid waste water in SAPO molecular sieve production |
| CN105753010A (en) * | 2014-12-19 | 2016-07-13 | 中国石油化工股份有限公司 | Preparation method of MWW structure molecular sieve |
-
2016
- 2016-09-08 CN CN201610811674.9A patent/CN106430228B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225772A (en) * | 2011-04-15 | 2011-10-26 | 大连理工大学 | Method for utilizing molecular sieve systhesis mother liquor |
| CN102502687A (en) * | 2011-10-18 | 2012-06-20 | 大连理工大学 | Method for greenly synthesizing Ti-Si molecular sieve |
| CN102491364A (en) * | 2011-12-01 | 2012-06-13 | 上海绿强新材料有限公司 | Method and device for recycling lithium from exchange waste fluid containing lithium |
| CN104743566A (en) * | 2013-12-26 | 2015-07-01 | 中国石油化工股份有限公司 | Method for recovering free template in molecular sieve slurry or filtrated stock |
| CN103723742A (en) * | 2013-12-31 | 2014-04-16 | 中国天辰工程有限公司 | Post-treatment method for washing, drying and calcining SAPO (silicoaluminophosphate) molecular sieve |
| CN203820665U (en) * | 2014-04-28 | 2014-09-10 | 中节能清洁技术发展有限公司 | Distilling recovery system for dimethylformamide rectification raffinate |
| CN105314757A (en) * | 2014-07-03 | 2016-02-10 | 中国石油化工股份有限公司 | Treatment method of mother liquid waste water in SAPO molecular sieve production |
| CN105753010A (en) * | 2014-12-19 | 2016-07-13 | 中国石油化工股份有限公司 | Preparation method of MWW structure molecular sieve |
| CN105198147A (en) * | 2015-09-15 | 2015-12-30 | 博天环境集团股份有限公司 | Treatment method for organic amine waste water generated by producing molecular sieve and carrier catalyst thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108569703A (en) * | 2017-03-10 | 2018-09-25 | 临沂大学 | A method of recycling mother liquor synthesizing Si-Al phosphorus molecular sieve |
| CN108569704A (en) * | 2017-03-10 | 2018-09-25 | 临沂大学 | A kind of Zeolite synthesis equipment |
| CN108569706A (en) * | 2017-03-10 | 2018-09-25 | 临沂大学 | A method of recycling mother liquor synthesizing Si-Al molecular sieve |
| CN109081362A (en) * | 2017-06-13 | 2018-12-25 | 神华集团有限责任公司 | The recovery method of remaining template during system with molecular sieve for preparing is standby |
| CN109305690A (en) * | 2018-10-17 | 2019-02-05 | 山东齐鲁华信高科有限公司 | Utilize the green synthesis method of recycling template and crystallization mother liquor synthesizing P-Al si molecular sieves |
| CN114433250A (en) * | 2020-10-16 | 2022-05-06 | 中国石油化工股份有限公司 | Slurry recovery device, slurry preparation system and slurry recovery method |
| CN114516644A (en) * | 2020-11-19 | 2022-05-20 | 中国石油化工股份有限公司 | Drying and crushing method of SAPO-34 molecular sieve |
| CN117582731A (en) * | 2024-01-18 | 2024-02-23 | 宿迁南翔化学品制造有限公司 | Multistage condensing distillation mechanism for large-scale malonic acid production |
| CN117582731B (en) * | 2024-01-18 | 2024-03-19 | 宿迁南翔化学品制造有限公司 | Multistage condensing distillation mechanism for large-scale malonic acid production |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106430228B (en) | 2018-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106430228B (en) | Molecular sieve mother solution processing method | |
| CN104829026B (en) | High salt high concentration cellulose ether sewage disposal system | |
| WO2006094437A1 (en) | A method and an multi-effect evaporation for waste water of alkylene oxides | |
| CN107188199A (en) | It is a kind of that ammonium sulfate, the Processes and apparatus of sodium sulphate are reclaimed from waste water | |
| CN207748878U (en) | A kind of recovery and processing system for sodium sulphate in high-salt wastewater | |
| CN108147489A (en) | Physical method pre-processes high concentration organic contaminant waster water process with high salt | |
| CN206508573U (en) | A kind of function of mechanical steam recompression evaporation and crystallization system of high-salt wastewater | |
| CN208917099U (en) | A kind of 2,3- dichloropyridine preparation separating methanol reclaimer | |
| CN104230077B (en) | The organic amine wastewater processing method of phosphorous aluminum silicon | |
| CN208151005U (en) | A kind of epoxy resin high-salt wastewater concentration purification system | |
| CN103253819B (en) | Production technology for treating ternary-monomer wastewater and extracting sodium sulfate | |
| CN104528850B (en) | Based on concentrated fresh water sea salt heat energy three co-generation systems of the sea water desalinization strong brine degree of depth | |
| CN108640392A (en) | A kind of water-oil separating treatment process | |
| CN105110396B (en) | Method and device for continuously separating low-boiling point substances in wastewater produced by extraction of natural gas and shale gas | |
| CN107098854B (en) | Ethoxyquinoline continuous production method | |
| CN105330886B (en) | A kind of method that polymer solvent NMP to producing PPTA reduces evaporation residue stickiness when being distilled to recover | |
| CN212151674U (en) | Liquid evaporation mummification processing apparatus | |
| US20230311024A1 (en) | Cooling device and cooling method for maltol sublimation section | |
| CN107697968A (en) | A kind of method and apparatus that bittern mineral is extracted using solar energy | |
| CN103922898B (en) | A kind of Resorcinol continuous crystallisation technique | |
| CN208054949U (en) | Rotary evaporator and low-temperature evaporation condensing crystallizing equipment | |
| CN206970384U (en) | A kind of Zero discharging system of desulfurization wastewater | |
| CN205386347U (en) | High strong brine of reuse of reclaimed water divides matter crystallization integrated equipment | |
| CN213254424U (en) | Condensation reaction equipment for producing rubber antioxidant DTPD | |
| CN204981538U (en) | Synchronous condensation of pyrolysis oil gas water and water oil separating recovery system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |