CN110548405A - High-pressure laminated hollow microporous ceramic membrane column - Google Patents
High-pressure laminated hollow microporous ceramic membrane column Download PDFInfo
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- CN110548405A CN110548405A CN201910844510.XA CN201910844510A CN110548405A CN 110548405 A CN110548405 A CN 110548405A CN 201910844510 A CN201910844510 A CN 201910844510A CN 110548405 A CN110548405 A CN 110548405A
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- 239000012528 membrane Substances 0.000 title claims abstract description 219
- 239000000919 ceramic Substances 0.000 title claims abstract description 156
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 283
- 239000008213 purified water Substances 0.000 claims abstract description 49
- 238000004140 cleaning Methods 0.000 claims abstract description 22
- 238000001914 filtration Methods 0.000 claims abstract description 19
- 238000000746 purification Methods 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 229910021389 graphene Inorganic materials 0.000 claims description 24
- 239000010865 sewage Substances 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 11
- 238000007789 sealing Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims 1
- 238000010030 laminating Methods 0.000 claims 1
- 238000005245 sintering Methods 0.000 claims 1
- 238000010304 firing Methods 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 32
- 238000000576 coating method Methods 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 230000008569 process Effects 0.000 description 13
- 235000020188 drinking water Nutrition 0.000 description 8
- 239000003651 drinking water Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000008399 tap water Substances 0.000 description 8
- 235000020679 tap water Nutrition 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 5
- 238000001223 reverse osmosis Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
- 229910010271 silicon carbide Inorganic materials 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000011001 backwashing Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000003673 groundwater Substances 0.000 description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- CGPYRTCBLCTOSW-UHFFFAOYSA-N [Hg].[P] Chemical compound [Hg].[P] CGPYRTCBLCTOSW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
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- 238000003903 river water pollution Methods 0.000 description 1
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- 239000013535 sea water Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000008279 sol Substances 0.000 description 1
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- 239000008107 starch Substances 0.000 description 1
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- 230000001954 sterilising effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000003442 weekly effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/08—Flat membrane modules
- B01D63/082—Flat membrane modules comprising a stack of flat membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/04—Backflushing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/16—Use of chemical agents
- B01D2321/162—Use of acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/16—Use of chemical agents
- B01D2321/164—Use of bases
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention discloses a high-pressure laminated hollow microporous ceramic membrane column, which comprises a column shell and a high-pressure membrane column, wherein the high-pressure membrane column is formed by stacking a plurality of inorganic ceramic disks, each inorganic ceramic disk is formed by butt-joint firing or bonding two identical inorganic ceramic membrane sheets with concave and convex parts, the inner surface of a cavity of each ceramic disk is a clean water surface, the outer surface of each ceramic disk is a raw water surface, only purified water flows in the cavity formed by the two clean water surfaces, and no raw water flows exist, the ceramic disk in the invention can be used in a high-pressure environment of less than or equal to 2MPa, compared with the existing filtering and permeating technology of the ceramic disk with 0.04MPa, the water production efficiency is improved by more than 30 times, the water production cost is reduced by 30 times, the ceramic disk also has the same service life of 10 years, the occupied area is small, the water production and management costs are low, and the cleaning is easy, so the ceramic disk is a substitute product of an organic membrane in the future water, can gradually replace the organic film product market monopolized by European and American countries for 20 years.
Description
Technical Field
the invention relates to the field of water treatment, in particular to a high-pressure laminated hollow microporous ceramic membrane column.
Background
MF, UF, NF and RO membranes widely used for water treatment at present are all organic membranes, the material of the NF and RO membranes is a composite membrane mainly made of polysulfone organic materials, the total thickness of an organic material lining body and a filter layer of the composite membrane is generally below 0.4mm, the thickness of a skin layer of the filter layer is only 10-40nm, the skin layer is thick, the high permeability of the membrane cannot be kept, and the strength of the thin filter layer is insufficient. In the process of backwashing and regeneration of the membrane, the cortex of the organic membrane is inevitably damaged, so that the service life of the organic membrane column is difficult to guarantee for more than 2 years under the full load condition, the water quality of the organic membrane column is usually fluctuated along with the pressure in the use process, the water quality is poor when the pressure is high, the water quality is good when the pressure is low, and the quality of finished water is always in a fluctuation state. In the process of seawater desalination, purified water output by an RO membrane can not reach the standard of direct drinking water, and due to unstable quality, products of all manufacturers are almost mixed with rainwater for precipitation and then filtered for drinking, although the acquired patent with the application number of 201610212990.4, namely microporous ceramic disks and filtering columns for water filtration, discloses a microporous ceramic disk and a filtering column for water filtration, as a plurality of holes need to be formed on a ceramic membrane, the ceramic membrane after the holes are butted to form the ceramic membrane disk, and raw water passes through the holes on the ceramic membrane disk layer by layer, so that the raw water is utilized to the maximum. This process works well, but there are cases where ceramic membranes are scrapped in large quantities and sealing fails when the ceramic disks are manufactured, resulting in mixing of raw and clean water. Thus, this patent is distinct from this patent.
The inorganic membrane mainly refers to a ceramic membrane, a glass membrane, a metal membrane, a molecular sieve carbon membrane or a mixed membrane of ceramic and metal, and the membrane is also classified into three membranes of MF, UF and NF according to the size of pores. The inorganic membrane has the characteristics of high strength, good thermal stability, good chemical stability, good cleaning state and easy regeneration and cleaning, so the inorganic membrane has long service life and has stability of about 10 years when being used in a water treatment process. But also acid and weak alkali resistance and high-pressure water washing resistance, so that the future development direction of the inorganic film is in the future.
Disclosure of Invention
The invention aims to provide a high-pressure laminated hollow microporous ceramic membrane column for water filtration, which solves the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
The high-pressure laminated hollow microporous ceramic membrane column comprises a column shell and a high-pressure membrane column installed in the column shell. Raw water flows into the raw water chamber through the raw water inlet, flows into the raw water cavity, enters the water purification cavity through the filtration of the raw water surface of the ceramic disc, converges through the water purification converging hole and flows out of the water purification outlet.
the raw water inlet pumps high-pressure raw water, the high-pressure membrane column is formed by stacking a plurality of ceramic disks, each ceramic disk is formed by connecting two ceramic membranes, the center of each ceramic membrane is provided with a water purification confluence hole and a central locking screw, two surfaces of each ceramic membrane are a raw water surface and a water purification surface respectively, a separation membrane layer is fired on the raw water surface, the separation membrane layer on the raw water surface is an UF membrane layer or an NF membrane layer coated with graphene, the raw water is filtered and permeated by the separation membrane layer on the raw water surface to obtain purified water, the ceramic disks coated with the UF membrane layer and the NF membrane layer coated with the graphene remove organic ions and inorganic ions larger than the diameters of membrane holes, the outer circle edges of the water purification surfaces of adjacent ceramic membranes are provided with water stopping grooves (circumference bonding grooves), a plurality of supporting bodies are arranged in the water purification confluence holes 204 of the adjacent ceramic membranes at intervals, and near-circle center bonding grooves, the water stopping groove is provided with bonding resin to prevent raw water from immersing into the water purifying cavity, the water stopping groove can also be coated with ceramic sealing materials, the 201b surfaces (water purifying surfaces) of the two ceramic diaphragms are oppositely sintered into a whole to form an integral ceramic diaphragm disc, and a rubber sealing ring groove 211 (used for installing a rubber sealing ring 203) is arranged beside the center hole of the raw water surface on the adjacent ceramic disc surface to prevent the raw water from flowing into the water purifying cavity. The adjacent ceramic plates are stacked through the structure, water purification cavities are formed in all hollow ceramic plate cavities, only water purification flows exist in the water purification cavities, raw water does not flow, a raw water cavity communicated with a raw water channel is formed between adjacent raw water surfaces, raw water flows into the water purification cavities through micropores of the raw water surfaces of the ceramic plates in a pressure permeation mode in the raw water cavities, and impurities are isolated out of the raw water surfaces and do not enter the water purification cavities during filtration.
The high-pressure membrane column is vertically arranged, the membrane column is in a state that a plurality of membrane columns work in parallel, and part of the membrane columns are in a cleaning state. The column shell is also provided with a sewage draining channel communicated with the raw water chamber, the sewage draining channel is provided with a sewage draining outlet, the sewage draining outlet is in a normally closed state when the membrane column is in a working state, and is in a normally open state when the membrane column is in a cleaning state.
The separation membrane layer is a UF ceramic membrane layer or a NF membrane layer coated with graphene, the pores of the UF ceramic membrane layer are 20-200nm, the pores of the graphene coating are 0.1nm ~ 2nm, and the separation membrane layer and the ceramic membrane are sintered to form a whole.
the raw water surface on be provided with the water conservancy diversion piece, form the raw water import between the adjacent water conservancy diversion piece, the water conservancy diversion piece one-to-one on the adjacent raw water surface, the water purification surface on be provided with the supporting shoe that the polylith is used for supporting, the supporting shoe one-to-one on the adjacent water purification surface, the water purification surface and the raw water surface of supporting shoe evenly distributed ceramic diaphragm on, be provided with the runner between the adjacent supporting shoe, the water purification chamber through this passageway and water purification convergent flow hole intercommunication, the water conservancy diversion piece set up towards water purification convergent flow hole slope, the raw water surface on be provided with a plurality of spaced supporting shoes, the supporting shoe can play the supporting role and make the raw water form turbulent state simultaneously, the raw water produces non-radial flow direction through the inclined plane of this water conservancy diversion piece, then forms the spiral.
the raw water cavity and the water purification cavity have pressure difference during filtration, the raw water is driven by the pressure difference to enter the water purification cavity through the pore filtration of the disc surface, and the raw water is converged by the water purification converging hole and then is discharged from the water purification outlet.
The flow guide block is obliquely arranged at an angle of 20-45 degrees facing the central hole, and the supporting blocks are uniformly distributed on the disc surface.
the invention has the beneficial effects that:
Compared with a patent 'micropore ceramic disc and filter column' with application number of 201610212990.4, the invention can coat separation coatings with various apertures, especially can coat and vacuum-sinter graphene coatings, and meanwhile, the ceramic membrane of the invention has no porous structure, thereby avoiding the conditions of easy cracking and incapability of ensuring surface flatness in the firing process, and further realizing the separation of raw water and purified water.
1. The ceramic membrane has the advantages that only purified water flows in the cavity formed by the two purified water surfaces, raw water does not flow, the raw water enters the raw water cavity from the raw water chamber, the filtered purified water enters the purified water cavity, and the filtered purified water flows out from the purified water outlet after converging through the purified water converging hole. Compared with the existing row-packed low-pressure flat plate type hollow ceramic membrane, the high-pressure laminated hollow microporous ceramic membrane column has larger raw water filtering area and higher water purification pressure, and further improves the water treatment efficiency.
2. the existing hollow flat membrane column is soaked in sewage or raw water, and purified water is obtained by 0.04MPa negative pressure swabbing; the high-pressure laminated hollow microporous ceramic membrane column is arranged in a high-pressure tank, and is pressurized by a water pump to perform pressure filtration on raw water. If the pressure of water supplied by the water pump is 1.2MPa, compared with the prior hollow flat membrane column, the ceramic membrane column with the same area can obtain 30 times of pure water in the same time.
3. Cleaning the membrane column: the steam-water backwashing can be carried out within 30 minutes in a short period. During the washing, after working for a long time, once weekly with acid-base washing, acid-base cleaning time respectively 30 minutes, and then the membrane column can be in 1 week above the time continuous operation, and the cleaning mode is simple, and it is less to wash the water yield, and the washing sewage still can recycle after handling, and the membrane column also can crisscross work, guarantees that the membrane column crowd is in incessant operating condition, has improved water purification efficiency, is applicable to large-scale water treatment.
4. The original water surface of the ceramic membrane is sintered with a coating layer, the ceramic filter layer with the aperture of 20nm-200nm or the graphene coating with the aperture of 0.1nm-2nm, the sintered filter layer has a high-strength inner tube surface and a high-strength filter layer, so that the high permeation quantity of the membrane is kept, the strength of the filter layer is ensured, and meanwhile, the high temperature of more than 80 ℃ can be borne, the cleaning of acid and weak base can be resisted, compared with the existing membrane, the membrane can bear larger water pressure, the longest service life is 10 times of that of an organic membrane column, and the ceramic membrane has longer service life and lower water production cost on the premise of ensuring the quality of purified water.
5. The graphene coating has a very thin structure, the pore diameter of the surface of the graphene coating is only 0.1nm-2nm, so that the raw water surface of the ceramic membrane is coated with the graphene coating with the thickness of 5nm-20nm and has the same water treatment function as an NF or RO reverse osmosis membrane, raw water pretreated by a UF membrane can be subjected to fine filtration by the NF membrane, and water can reach the standard of direct drinking water after being subjected to reverse osmosis treatment and disinfection by the graphene ceramic membrane.
The ceramic disc designed in the invention can be used in a high-pressure environment of 1-2MPa, and compared with the existing filtering and permeating technology of the ceramic disc of 0.04MPa, the water making efficiency is improved by 30 times, the water making cost is reduced by 30 times, and the ceramic disc also has the same service life of 10 years. The high-pressure ceramic disc membrane column has small floor area, low water production and management cost and easy cleaning, thereby being a substitute product for the future water treatment industry and gradually replacing the organic membrane product market monopolized by European and American countries for 20 years.
Drawings
FIG. 1 is a schematic structural view of a ceramic membrane column assembled by 120 ceramic disks under the locking of a central locking screw, placed in a column shell and vertically placed;
FIG. 2 is a partial cross-sectional view of a column jacket according to the present invention;
FIG. 3 is a schematic structural view of the two lowermost ceramic disks of the present invention after being stacked;
FIG. 4 is a schematic structural view of the raw water surface of the ceramic diaphragm of the present invention;
FIG. 5 is a schematic structural view of the clean water surface of the ceramic diaphragm of the present invention;
FIG. 6 is a side cross-sectional view of a ceramic diaphragm of the present invention;
FIG. 7 is an enlarged view of a portion of the invention at A;
FIG. 8 is a partial enlarged view of the present invention at B;
FIG. 9 is a schematic view showing the structure of a ceramic disk Y according to the present invention;
FIG. 10 is a schematic structural view of a ceramic diaphragm according to the present invention;
FIG. 11 is a schematic view of the center structure of the ceramic diaphragm of the present invention.
In the figure, a column shell 1, a high-pressure membrane column 2, a raw water inlet 101, a purified water outlet 102, a raw water chamber 103, a purified water cavity 104, a sewage discharge outlet 105, a ceramic membrane 201, a raw water surface 201a, a purified water surface 201b, a circumferential bonding groove 202, a rubber sealing ring 203, a purified water converging hole 204, a raw water cavity 205, a mounting hole 206, a supporting block 207, a flow guide block 208, a central locking screw 209, a near-circle-center bonding groove 210, a rubber sealing ring groove 211, a stainless steel locking plate 212 and permeable polyester cotton 213 are arranged in the column shell.
Detailed Description
The technical solutions of the present invention are further described in detail below with reference to the accompanying drawings, but the scope of the present invention is not limited to the following.
referring to fig. 1 to 11, the present invention provides a microporous ceramic membrane disk fired at a temperature of 1300 ℃ or higher, and the upper and lower surfaces of the microporous ceramic membrane disk are coated with a coating layer (separation membrane layer) respectively, wherein the coating layer is a ceramic filter layer having a pore size of 20nm to 200nm or a graphene coating layer having a pore size of 0.2nm to 2nm, and the coating layer and the microporous ceramic disk are sintered into a whole, wherein the graphene film is fired in a vacuum environment.
the membrane discs are connected into a high-pressure membrane column through a central locking screw, a plurality of membrane discs are assembled into a filter column with large surface area, hundreds of hollow laminated ceramic membrane discs can be stacked into a membrane column with a circular section or other shapes by using the process, and the area of a single membrane column can reach 10m2-100m2The filter column of (1). The novel ceramic membrane hollow laminated assembly process can be used for assembling the microporous ceramic membrane into a high-pressure membrane column, and can effectively replace the organic membrane column which is popular in the market.
The preparation method of the high-pressure flat plate hollow laminated ceramic membrane column comprises the following steps:
the hollow flat inorganic membrane is mainly made of two ceramic membrane materials of aluminum oxide and silicon carbide, and other carbon fiber membranes and metal mixed membranes are the same firing process, except that the carbon fiber-containing material is fired in vacuum, which is not exemplified.
Preparing a ceramic flat membrane: mainly adopts extrusion molding and compression molding, and the materials mainly comprise silicon carbide, titanium dioxide, aluminum oxide and the like. Firstly, a membrane inner tube (ceramic membrane) of a flat membrane is manufactured, taking an alumina ceramic membrane as an example, the alumina ceramic membrane is used as a main material and is prepared by adopting alumina, mixed alumina sol, silica gel and starch as pore-forming agents and adopting an extrusion molding process. And after drying, coating the separation film layer.
Preparation of a separation membrane layer: the micro powder of the alumina, the polyacrylic acid, the water and other additives are stirred and mixed according to the proportion of 1:0.5:1: 0.2.
Completely soaking the original water surface of the dried ceramic flat plate supporting block in liquid for 5s, drying the formed film layer at 40-60 ℃, and then implanting the dried formed film layer into a shuttle kiln for firing, wherein the forming temperature of the aluminum oxide ceramic membrane is 1350-1400 ℃. If the supporting block material is silicon carbide, the firing temperature is 1600 ℃; if the support block material is carbon fiber, then two firings are performed: and after the ceramic disc blank is fired, coating a graphene coating on the surface, and performing secondary firing, wherein the vacuum firing temperature is 1000 ℃.
examples are: a production process for manufacturing a flat plate type microporous hollow ceramic membrane. As shown in FIG. 4 and FIG. 5, the disk ceramic membrane has a diameter of 314mm and a thickness of 4mm, and is formed by firing alumina or silicon carbide, and has a surface 201a contacting raw water and a surface 201b permeating purified water. The 201b faces of the two diaphragms are bonded or sintered together to form a ceramic disc (Y-disc). The depth of the concave cavity of each 201b surface is 0.8mm, so that the two 201b surfaces are bonded together to form a Y-shaped disc with a cavity with the height of 1.6mm, and clean water can be collected through the cavity 104 and collected in the clean water collecting hole 204. The diameter of the purified water converging hole is 10mm, the semicircular surface is locked on a shaft through a central locking screw 209 and 120Y discs, the central locking screw 209 is a solid shaft with phi 42mm, the 120Y discs are tightly fixed together by stainless steel locking plates 212 at two ends of the central shaft to form a membrane column, the membrane column is then arranged in a high-pressure stainless steel column shell 1 with phi 356 x 3mm (the joint of the membrane column and the high-pressure stainless steel column shell 1 is also provided with permeable polyester cotton 213) to lock the central locking screw 209, and a raw water outlet 101 and a purified water outlet 102 are connected to form the high-pressure laminated hollow microporous ceramic membrane column, as shown in figure 1.
The raw water flow direction of the high-pressure laminated hollow microporous ceramic membrane column is as follows:
Raw water flow direction: raw water flows into the raw water chamber 103 through the raw water inlet 101, flows into the raw water chamber 205, is filtered by the raw water surface 201a of the ceramic disc, enters the purified water chamber 104, is converged by the purified water converging hole 204, and then flows out from the purified water outlet 102.
The structure of the high-pressure laminated hollow microporous ceramic membrane column is as follows:
The structural form of the ceramic disc is as follows:
The ceramic membrane has a raw water surface 201a and a purified water surface 201b, wherein the raw water surface 201a (shown in fig. 4) is a layer surface into which raw water W0 flows, the purified water W1 is a layer surface on which purified water W1 converges, the surface 201b is a concave surface, and the depth h of the inner cavity is =0.8 mm.
The two surfaces 201b of the two ceramic membranes are bonded together before assembly into a ceramic membrane column, or may be fired together, and each ceramic membrane disk may be stacked through mounting holes 206 prior to bonding or firing. Due to the special structure of the 201b surfaces, after the two 201b surfaces are bonded together, a ceramic disc Y with the disc thickness of 8mm is formed, the diameter of the ceramic disc Y is phi =314mm, and the thickness t =8 mm.
As for other specifications of the ceramic diaphragm, there are now available φ 200, φ 314, φ 400 disks, and other specifications of disks should be within the scope of protection.
The outer circumference of the ceramic disc Y is isolated from the outside, and raw water cannot enter the inner cavity of the ceramic disc Y through a gap on the outer circumference of the ceramic disc Y. Meanwhile, due to the special structure of the surface 201b, the bonded ceramic disc Y is a cavity, the thickness of the cavity in the ceramic disc Y is 1.6mm, and the thickness is enough for pure water to flow through the pure water converging hole 204 in the center of the circle of the inner cavity of the ceramic disc to converge.
Because the diameter of the membrane pores of the UF ceramic disk Y is 20-200nm, raw water flows through the upper surface 201a and the lower surface 201a of the ceramic disk Y, the raw water surface 201a is also concave, and the depth h of an inner cavity is =0.8 mm. Two adjacent 201a surfaces form a raw water cavity with the height of 1.6 mm. An inner sealing ring 203 arranged at the central round hole of the surface 201a prevents raw water from entering a purified water cavity 204. Under the action of pressure, clean water can only be mechanically filtered through membrane holes, enters the clean water cavity 104 from the surface 201a of the ceramic disc Y and flows out through the clean water collecting hole 204 in the center of the ceramic disc Y, the bearing condition of the ceramic disc under the pressure is fully considered by the structures of the surfaces 201a and 201b of the ceramic membranes, and supporting blocks 207 with the diameter phi of 3mm and the height equal to the disc surface are arranged on the surfaces 201a and 201b of the ceramic membranes, so that the support of the two surfaces 201b in the Y disc and the support of the Y disc with other Y discs after the Y disc is stacked are mainly ensured. The central circular hole is provided with a semi-circular groove 301 (refer to fig. 11) with the diameter of 10mm, which is used for flowing out clean water. Compared with the published patent 'micropore ceramic disc and filter column for water filtration' with the application number of 201610212990.4, because the 'raw water vertical outward channel (1.2) in the outflow disc' mentioned in the patent does not exist, only the flow of purified water exists in the cavity formed by the two 201b surfaces, and the flow of raw water does not exist, so that the raw water enters the raw water inlet 101 for filtration once and then the purified water flows out from the purified water outlet 102, the raw water does not need to be filtered for multiple times, the structure of the ceramic disc is simplified, and the efficiency is improved.
Secondly, lamination type hollow microporous ceramic membrane column:
120Y discs with the thickness of 8mm are assembled into a membrane column by a special assembly process, the membrane column is placed in a high-pressure resistant stainless steel cylinder, and a water inlet and a water outlet are reserved. Raw water flows into the cylinder through the water inlet, enters the raw water surface of the ceramic disc in the membrane column, and is filtered and permeated through pressure. The purified water flows out after being collected by the water outlet, enters the water storage tank after being disinfected by ultraviolet rays or ozone, and then enters the user terminal.
If the surface area of the purified water in the high-pressure ceramic membrane column is 20m2if the diameter of the micropores on the disk surface is 20nm and the water pressure is 0.04MPa, carrying out water treatment capacity of 1m each hour; if the water pressure is 1.2MPa, the water treatment capacity per hour is 30m, and the water treatment efficiency of the high-pressure laminated microporous hollow ceramic membrane is high enough.
1. The filtration principle is as follows:
Fig. 1 shows a high-pressure membrane column assembled by 120Y disks, when raw water enters a stainless steel column shell 1 from a raw water inlet 101, the pressure in the column shell 1 gradually rises, so that pressure is formed on the surface 201a of a stacked ceramic disk Y, the raw water enters the surface cavity 201b through a part of a filter layer of the surface 201a to form purified water, the other part of the raw water is diluted by new raw water, the process is continued until the impurity concentration of the raw water in the whole stainless steel column shell 1 is increased to be more than 30%, at this time, the membrane column enters a cleaning procedure, and other membrane columns connected in parallel start to work. The permeability of the purified water can reach more than 90% by the plurality of membrane columns which are connected in parallel and work intermittently. The cleaned waste water is discharged into a waste water tank, and the flocculated raw water is recycled, so that the yield of purified water can reach more than 95% of the raw water, and the water production efficiency is greatly higher than that of an organic membrane.
2. the cleaning principle is as follows:
When the filtration rate of any one membrane column is reduced by 30%, the membrane column stops working and enters a cleaning state, and other membrane columns connected in parallel continue working, so that purified water can continuously flow out.
Only the vapor-water backwashing is needed in a short time. The cleaning time is within 30 minutes. The soda water is cleaned as follows: firstly, pure water containing compressed air enters a membrane column through a pure water outlet 102, the membrane column is backwashed, scales on the surface 201a of the ceramic disc Y are cleaned, and the washing water takes away the scales and flows out through a drain outlet 105;
After long-time work, the cleaning is carried out once a week by using acid and alkali, and the acid and alkali cleaning time is 30 minutes respectively. The cleaning method comprises the following steps:
Cleaning inorganic substance with 5% dilute nitric acid, cleaning organic substance with 5% NaOH, soaking and washing with clear water, and performing the second working cycle.
The membrane column can be operated continuously for 24 hours. In Chengdu regionFor example, if the groundwater is treated by a ceramic membrane column, the groundwater can be continuously cleaned by acid and alkali for 2 weeks under the working condition of 1.2 MPa. The amount of water for cleaning is small, and the water can be recycled after treatment. The membrane columns can also work in a staggered mode, so that one part of the membrane columns are in a working state, and the other part of the membrane columns are in a cleaning or closing state.
Not only can the hollow ceramic membrane have a laminated structure, but in practice, ceramic membranes, glass membranes, metal membranes, molecular sieve carbon membranes or mixed membranes of ceramic and metal can be designed into the hollow laminated membrane column structure. The membrane column composed of the hollow ceramic membranes is only a representative product, and the maximum use value of the stacked membrane column is that the raw water can be pretreated in a large scale at low cost, and the quality of the discharged water can be ensured for a long time. Therefore, the membrane column formed by the hollow ceramic membranes has high use value, and the glass membranes, the metal membranes, the molecular sieve carbon membranes or the mixed membranes of the ceramic and the metal can form the stacked membrane column by the same process, so that the membrane column also has high use value.
Thirdly, coating the graphene:
the graphene coating has a very thin structure, and the pore diameter of the surface of the graphene coating is only 0.1nm-2nm, so the ceramic membrane coated with the graphene coating or the membrane made of other materials has the same water treatment function as RO, and water can reach the standard of direct drinking water (CJ 94-2005) after being subjected to reverse osmosis treatment and sterilization by the graphene ceramic membrane.
the structure of the high-pressure laminated hollow microporous ceramic membrane column is shown in figure 1. The combination of membrane column is that 120 pieces of ceramic dish Y constitute, and the membrane column can bear the high temperature of more than 80 ℃, can be able to bear the washing of acid and weak base, consequently has longer life and lower system water cost under the prerequisite of guaranteeing the quality of water purification.
reviewing the condition of tap water drunk by each urban resident now, the tap water comes from river water, the river water pollution mainly comprises ammonia nitrogen pollution, inorganic matter, phosphorus mercury pollution and various metal salt sediments, and various organic and inorganic flocculants are frequently added for removing the substances, so that the water source is polluted. Indexes of tap water in China and tap water in the United states are greatly different, most of tap water in the United states comes from large-scale reservoir water intake, the water is precipitated for many years, NTU is very small, the amount of precipitate and sludge is only 10ppm, which is one hundred thousand of the water intake, so that a chemical treatment agent required for treatment is very small, and excessive secondary pollution is not caused. If Chinese tap water is treated by the ceramic membrane osmosis reverse osmosis, the water quality of the tap water can reach the standard of the tap water in the United states. This is essential to the health of Chinese people.
however, the cost of drinking water prepared by foreign organic NF (RO) membranes is 2-4 yuan per ton, if the drinking water is replaced by the hollow ceramic membrane stacked membrane column used by the invention for pretreatment, the pretreated raw water can reach the standard of direct drinking water through the permeation and reverse osmosis of the stacked hollow ceramic membrane column covered with the graphene coating. The cost of the latter can be reduced to 0.2 yuan per ton of water, so that the product is a necessary product for solving the drinking water of Chinese people in the future. The life quality of Chinese people is greatly improved, and the average life of residents is prolonged by more than ten years. The graphene water purification problem is also a major problem which is proposed to be solved by the United nations health administration in the next decade to all countries in the world and a major problem which needs to be solved by the Chinese government. Therefore our invention will be a significant contribution to improving human life.
The diameter of a membrane coated with graphene hollow ceramic developed by people at present reaches 400mm, the equivalent membrane area of a membrane column is above 40m2, one membrane column can produce more than 8.5 tons of purified water per hour, one membrane column can produce 200 tons of purified water per day, and 1 ten thousand membrane columns can produce 200 ten thousand tons of purified water per day, so that the requirement of large city drinking water similar to Beijing is met.
In addition, the high-pressure laminated hollow microporous ceramic membrane column can also solve the large-scale and large-area sewage treatment problems (such as oil field sewage and offshore oil leakage); the high-pressure laminated hollow microporous ceramic membrane column can also really solve the problem of reclaimed water reuse; the laminated ceramic membrane column covered with the graphene coating can be used for intercepting leaked sewage of a nuclear power station, and the laminated ceramic membrane column is the only solution for pollution of nuclear leaked water worldwide.
Claims (5)
1. a high-pressure laminated hollow microporous ceramic membrane column comprises a column shell (1) and a high-pressure membrane column (2) installed in the column shell (1), wherein a raw water inlet (101), a purified water outlet (102), a raw water chamber (103), a raw water chamber (205), a purified water outlet (102) and a purified water chamber (104) are arranged on the column shell (1), the high-pressure membrane column is characterized in that the high-pressure membrane column (2) is formed by laminating a plurality of ceramic disks, the ceramic disks are formed by oppositely bonding or sintering the purified water surfaces (201 b) of two identical ceramic membranes (201), a purified water converging hole (204) is arranged in the center of each ceramic membrane (201), the two surfaces of each ceramic membrane (201) are respectively a raw water surface (201 a) and a purified water surface (201 b), a separation membrane layer is fired on the raw water surface (201 a), the separation membrane layer on the raw water surface (201 a) is a UF membrane layer or a NF membrane layer coated with graphene, and a circumferential bonding groove (202) is arranged at the edge of the purified water surface (201 b, raw water on the outer circumference of the ceramic disc can be prevented from flowing into the water purification cavity (104) through the bonding position of the ceramic diaphragm after bonding, a rubber sealing ring (203) is arranged beside a central hole of a raw water surface (201 a) of the ceramic diaphragm (201), a purified water converging hole (204) communicated with the water purification cavity (104) is formed between adjacent purified water surfaces (201 b), only purified water flows in the water purification cavity (104) and does not flow, a raw water cavity (205) is formed between adjacent raw water surfaces (201 a), raw water flows into the water purification cavity (104) through micropores of the ceramic diaphragm (201 a) in the raw water cavity (205) in a pressure permeation mode, impurities are isolated outside the raw water surface (201 a) during filtration and do not enter the water purification cavity (104), and a sewage flow channel is not formed during filtration.
2. The high-pressure laminated hollow microporous ceramic membrane column according to claim 1, wherein the high-pressure membrane column (2) is vertically placed, and the high-pressure ceramic membrane column is in a state that a plurality of membrane columns work in parallel and the membrane columns in work are in an interval cleaning state.
3. the high-pressure laminated hollow microporous ceramic membrane column as claimed in claim 1, wherein a sewage draining channel communicated with the raw water chamber (103) is further arranged on the column shell (1), a sewage draining outlet (105) is arranged on the sewage draining channel, the sewage draining outlet (105) is in a normally closed state when the membrane column works, and is in a normally open state when the membrane column is cleaned.
4. The high-pressure laminated hollow microporous ceramic membrane column according to claim 1, wherein the separation membrane layer is a UF membrane layer having a pore size of 20nm to 200nm or a NF membrane layer having a pore size of 0.1nm to 2nm coated with graphene, and the separation membrane layer is sintered integrally with the raw water surface (201 a) of the ceramic membrane.
5. The high-pressure laminated hollow microporous ceramic membrane column according to claim 1, wherein a raw water inlet (101) of the raw water surface (201 a) is provided with a flow guide block (208) for supporting and backflow, a raw water inlet is formed between adjacent flow guide blocks (208), a plurality of supporting blocks (207) which are separated by 15-25mm and used for supporting are arranged on the raw water surface (201 a) and the clean water surface (201 b), and the supporting blocks (207) on the raw water surface (201 a) of the adjacent ceramic disks correspond to each other; similarly, the supporting blocks (207) on the adjacent clean water surfaces (201 b) correspond one to one, the supporting blocks (207) are uniformly distributed on the disc surface, a water flowing channel is arranged between the adjacent supporting blocks (207), the clean water cavity (104) is communicated with the clean water converging hole (204) through the channel, the flow guide block (208) is obliquely arranged towards the central hole, raw water generates a non-radial flow direction through the inclined surface of the flow guide block (208), and then spiral fluid is formed on the raw water cavity (205) through the flow guide of the supporting blocks (207).
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