EP2556017A2 - Method for the production of hydrogen and other products and device for carrying out this method - Google Patents
Method for the production of hydrogen and other products and device for carrying out this methodInfo
- Publication number
- EP2556017A2 EP2556017A2 EP11728765A EP11728765A EP2556017A2 EP 2556017 A2 EP2556017 A2 EP 2556017A2 EP 11728765 A EP11728765 A EP 11728765A EP 11728765 A EP11728765 A EP 11728765A EP 2556017 A2 EP2556017 A2 EP 2556017A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- hydrogen
- tank
- fed
- water
- reactor
- 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.)
- Withdrawn
Links
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 205
- 239000001257 hydrogen Substances 0.000 title claims abstract description 204
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 193
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 39
- 229910001868 water Inorganic materials 0.000 claims abstract description 134
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 133
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 113
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 104
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 101
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims abstract description 90
- 239000011780 sodium chloride Substances 0.000 claims abstract description 52
- 239000004411 aluminium Substances 0.000 claims abstract description 39
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000011049 filling Methods 0.000 claims abstract description 17
- 239000002699 waste material Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 9
- 229910001679 gibbsite Inorganic materials 0.000 claims description 64
- 239000012295 chemical reaction liquid Substances 0.000 claims description 56
- 238000005406 washing Methods 0.000 claims description 41
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 39
- 239000012716 precipitator Substances 0.000 claims description 24
- 238000000926 separation method Methods 0.000 claims description 19
- 239000000498 cooling water Substances 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 16
- 230000003472 neutralizing effect Effects 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000012856 packing Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 238000007710 freezing Methods 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 241000446313 Lamella Species 0.000 claims description 4
- 238000012958 reprocessing Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 230000005294 ferromagnetic effect Effects 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 239000007791 liquid phase Substances 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 238000009738 saturating Methods 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 10
- 238000000746 purification Methods 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 230000002349 favourable effect Effects 0.000 description 24
- 239000002360 explosive Substances 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 229910018626 Al(OH) Inorganic materials 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 241000478345 Afer Species 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 240000002129 Malva sylvestris Species 0.000 description 1
- 235000006770 Malva sylvestris Nutrition 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 244000299461 Theobroma cacao Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- -1 bottle caps Chemical compound 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical class [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 235000019219 chocolate Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 235000020186 condensed milk Nutrition 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 125000000914 phenoxymethylpenicillanyl group Chemical group CC1(S[C@H]2N([C@H]1C(=O)*)C([C@H]2NC(COC2=CC=CC=C2)=O)=O)C 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 235000013618 yogurt Nutrition 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
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/08—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents with metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/002—Avoiding undesirable reactions or side-effects, e.g. avoiding explosions, or improving the yield by suppressing side-reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
- B01J19/0066—Stirrers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J7/00—Apparatus for generating gases
- B01J7/02—Apparatus for generating gases by wet methods
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/14—Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/14—Purification
- C01D3/16—Purification by precipitation or adsorption
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/42—Preparation of aluminium oxide or hydroxide from metallic aluminium, e.g. by oxidation
- C01F7/428—Preparation of aluminium oxide or hydroxide from metallic aluminium, e.g. by oxidation by oxidation in an aqueous solution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00004—Scale aspects
- B01J2219/00006—Large-scale industrial plants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
- B01J2219/00094—Jackets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00162—Controlling or regulating processes controlling the pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00245—Avoiding undesirable reactions or side-effects
- B01J2219/00259—Preventing runaway of the chemical reaction
- B01J2219/00263—Preventing explosion of the chemical mixture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00245—Avoiding undesirable reactions or side-effects
- B01J2219/0027—Pressure relief
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Definitions
- This invention relates to a method of industrial production of hydrogen and other products from waste aluminium and devices for the method.
- waste material in this case aluminium, (aluminium packaging, lids, tubes, closures, beverage cans etc.) is a global issue.
- Hydrogen production from, the reaction of ⁇ luntimurn. with water using .sodium hydroxide as, a catalyst is generally known.
- the products of the reaction are A1 2 0 3 or Al(OH 3 ) and heat.
- Waste aluminium can be used favourably for production.
- the patent file CN 183 6773 introduces a catalyst applied to aluminium waste to remove the protective layer on the surface of aluminium for an improved reaction of aluminium with water.
- the catalyst is a compound containing PVA, ethanol, acetone, mercury chlorides and water.
- aluminium is used in particular as well as alloys of alkali, metals, aluminium, alloys, magnesium alloys, lithium alloys, etc.
- the raw material (fuel) is in the form of dust, powder, compressed boards or cell cartridges.
- Patent file US 6506 360 describes a small compact device for hydrogen production by which the fuel (ground waste aluminium) is fed to a reactor in a fuel cell where it reacts with water in the presence of NaOH as a catalyst with hydrogen and heat production. The intensity of the reaction is controlled by immersion of the fuel cell to avoid overheating of the reactor. The generated heat is not used in any way, and the hydrogen is combusted in a burner.
- the device may be used e.g. as a cooker, it is not suitable for hydrogen production at an industrial level. For hydrogen production at' an industrial level, the device described in patent file DE 340 1194 is used.
- Production takes place in a reactor in the form of a reaction of aluminium in the presence of NaOH as a catalyst with heat, hydrogen and DC current being generated while natrium-aluminate is generated as a by-product.
- Aluminium raw material is placed on a mesh in the reactor; NaOH and water are fed to the reactor through a central funnel then rises above the mesh where it reacts with aluminium.
- the hydrogen is removed and a DC electric current is taken from the electrode arranged inside the reactor.
- a method for the use of heat is not described in detail, but the reactor shell is fitted with a water heat exchanger used for the heating of water and cooling of the reactor at the same time. Natrium- aluminiate is described here as a.
- the task of the invention is to establish a method and device fpr, the production of hydrogen and other products from waste aluminium which, would remove .all the issues described above, which would be safe as well as suitable for the production , of hydrogen at industrial levels, environmentally- friendly (waste-free), and economically effective.
- the objective as specified above is achieved by the method of the production of hydrogen and other products in a reactor by the reaction of aluminium with water in the presence of sodium hydroxide; or potassium hydroxide as a catalyst, according to the presented invention, the basis of which is that the reactor, and/or other accessory devices are depressurized to a negative pressure at least 0.5 kPa with a vacuum pump before the reaction, the reactor is then filled with hydrogen of a minimum purity of 99.8%, the gas is pumped away again with a subsequent filling with hydrogen of a minimum purity of 99.5% again to positive pressure at least 0.1 MPa, whereas the gas removed from the reactor and/or accessory equipment using the vacuum pump is exhausted to, . a . chimney and dispersed into the atmosphere.
- the underlying idea of the invention is the increased safety of hydrogen production in which a safe level must be achieved by exhausting all air from the production device before production, when the oxygen content in the finished hydrogen does not exceed 10 ppm.
- the produced hydrogen is further purified so that the hydrogen produced in the reactor is washed in washing tank in treated service deaerated water and saturated with hydrogen.
- the hydrogen is fed to the washing tank through small holes to aerate in the water column.
- Ferromagnetic admixtures are separated from the reaction liquid, being the mixture of water, NaOH, and aluminium particles, with the use of a solenoid in the tank, the liquid is then fed to the input of a mechanical filter where the mechanical admixtures are separated, then the liquid is fed to the. input of the first 'precipitator of Al(OH) 3j where aluminium hydroxide is precipitated wkh the use of hydrochloric acid and the suspension thus
- the steps towards the final, purification of ⁇ sodium; hydroxide and, separation of salt solution are performed and , the salt solution will. be. used for the next applicable product sodium chloride, so that aluminium hydroxide from the second filter Al(OH) 3 mixes with water in the, washing tank Al(OH) 3 and NaCl contained, in the suspension is dissolved, the suspension is then deposited, the salt solution is fed t the third Al(OH)3 filter;, the tank is filled with water again and the sediment is mixed after analysis in the presence : of I TaCl; the washing process then either repeats or the suspension is fed to the third Al(OH) 3 filter. ,
- hot water be used for operation of the device from the water heat exchanger of the reactor, which is fed to the hot service water tank, from which hot service water is fed to the hot service water tank, from which hot service water is distributed to the second Al(OH)3 precipitator, NaCl crystallizing device and NaCl dryer.
- the inner space,;pf the reactor, low-pressure hydrogen tank and service tank is connected to a vacuum pump and its output is fed to a chimney while at the same time, the feactor, the hydrogen tank and, service tank are independently connected to the chimney via safety valves.
- Connection with, the vacuum pump is used for rinsing the tanks and pumping gas away, a direct connection with the chimney via the safety valves is a safety measure for the case of unexpected and dangerous overpressure in the reactor or another accessory device.
- the issue of service hydrogen required for rinsing of the device is addressed so that the low-pressure hydrogen tank is connected to the medium-pressure service hydrogen tank via the medium- pressure compressor for washing of the reactor and operation tanks for production and treatment of hydrogen and other products for treatment of the; reaction liquid.
- the low- pressure hydrogen tank is connected to high-pressure hydrogen tank via high-pressure compressor from which the compressed'hydrogen is fed to the filling and distributing point of hydrogen.
- Hydrogen can be distributed e.g. in pressure cylinders or otherwise as requested by customer.
- Another of potentially possible method of use of hydrogen produced and treated in this way is re-compressing and use for combustion engine in mixture with oxygen, whereas the combustion engine may drive an alternator or a generator for production of electricity sold to the distribution grid.
- the clean reaction liquid is furthermore reprocessed for reuse, whereas the output of the cleaft reaction . liquid is connected from the inter-tank of the reaction liquid to the input, of reprocessed reaction, liquid tank, whereas the tank is connected with the first tank of sodium hydroxide and the output pf the reprocessed reaction liquid is fed back to the reactor input from the tank,, .. . . , ,
- the device according to the' invention includes a reservoir for cooling water, which is connected with hot water heat exchanger, with washing tank and deaeration and saturation tank.
- ⁇ '" ⁇ ' ⁇ " ⁇ ⁇ the device is modified for the final purification and sale of pure aluminium hydroxide so that output of the reaction liquid from the inter-tank of the reaction liquid; and reprocessed reaction liquid from the tank of the reprocessed reaction liquid is fed to the neutralizing unit connected with the second hydrochloric acid tank and output of the neutralized suspension from the neutralizing unit is fed to input of the first Al(OH);.
- sodium chloride as the final product for sale is prepared.
- Solution of sodium chloride from the first Al(OH).3 filter is fed to the NaCl crystallizing unit from which the crystallized sodium chloride transferred to NaCl store for dispatch via the NaCl dryer.
- the NaCl crystallizing unit is formed at least from one bath with hot service water feed from hot service water tank, fitted with skirrimer of salt steams terminated in a condenser.
- the main input raw material for . hydrogen production is waste aluminium, e.g. bottle caps, lids from yoghurts, pastes and similar products, tubes from condensed milk, packaging from chocolates, butter etc., beverage cans, cream jars, packaging of cheeses and much more.
- This waste material is collected in collection and gathering place 43 of aluminium located outside so-called hydrogen zone, i.e. the zone of the main production equipment where aluminium is produced. From there, aluminium; is transported to sorting , and crushing line 40 also located outside the hydrogen zone.
- aluminium is manuall checked to remove plastic materials, paper etc.
- This sorted waste is transported to an incinerator. Aluminium is then crushed into 4 - 6 mm particles and stored iri. crushed aluminium storage 4J_ that may be located outside the hydrogen zone as well.
- crushed aluminium is transported to filling and dosing device 7, which is already located in the hydrogen zone, and its bin and other components are air-displaced before each operation as any other device in the hydrogen zone.
- the bin of the filling and dosing device 7 is filled with belt conveyor; filling of .crushed aluminium to the reactor I is automatic using a screw-dosing conxeyor.
- Another raw material for hydrogen production is water. Water is pumped from the water pipeline, goes through the water treatment plant 44 and collects in the reservoir 23 of the cooling water located outside the hydrogen zone, from where it is fed primarily to the reactor 1 as well as other parts of the device as described later.
- the next raw material for hydrogen production is sodium hydroxide purchased and stored in the first bin 20 of sodium hydroxide in hydrogen zone from which it is fed to the tank J_9 for reprocessing of the reaction liquid (mixture of sodium hydroxide and water) and then to the reactor I .
- Sodium hydroxide is stored also in the second bin 37 of sodium hydroxide outside the hydrogen zone;'
- the last raw material required 1 for hydrogen production according to the invention is hydrochloric acid collected in the first reservoir 15 of hydrochloric acid in the hydrogen zone and in the second reservoir 36 of hydrochloric acid outside the hydrogen zone and it is used for Al(OH) 3 precipitation and neutralization of the reaction liquid.
- the hydrogen production occurs in the hydrogen zone depicted on figure 1 as the area delimited with dashed line and includes all important devices used for production of hydrogen, particularly the reactor I ,
- the reactor is a closed container in which known chemical reaction for hydrogen production occurs:
- Hydrogen generated in the reactor 1 is removed for washing in the washing tank 6 and the reaction liquid (mixture of H 2 0 and NaOH with aluminium residues) is removed for separation of metal particles to the tank with solenoid 1_1.
- the reaction 'must be 1 mterrupted immediately 'by feeding of cold Hvafdr 1 firbitf the 1 reservoir ⁇ ! f '- ⁇ ⁇ emergency and service'- wafer' and charge of more aluminium frtirri the fil ' lirtg and dbs ri ! line '7 is stopped.
- the reactor 1 is designed ' to negative pressure at ; least 0,5 kPa and positive pressure- 1 MPa. ' ⁇ ⁇ - : - - ⁇ ; r : : 1 " - ⁇ ⁇ 1 ' - ' ' ⁇ il nrA ; .
- the reactor I as well as filling " ancl dosing line 7 ⁇ as well as all other devices in so- called hydrogen zone are interconnected with the vacuum pump 4 so that ihpiuts from each device are fed to the collection pipeline VP.
- the vacuum pump 4 With the use of the vacuum pump 4 the production line must be successively (tank by tank) air-displaced to negative pressure; about 1.3 kPa and subsequently filled with pure hydrogen of at least #9.5% purity before.each time the production line is started or after opening of a tank during operation. This is hydrogen identified as "H 2 rinse” taken from medium-pressure reseryoir 24 of the service hydrogen and distributed to each reservoir in the hydrogen zone.
- each reservoir in the hydrogen, zone is air-displaced again and filled with "H 2 rinse” hydrogen to positive pressure of 0, 1 MPa. All exhausted air as well as rinse hydrogen is taken to the chimney 5 to which the output from the vacuum pump 4 terminates. This process is necessary for safety reasons; exhausting of all air must provide oxygen contents in finished produced hydrogen under 10 ppm.
- the chimney 5 consists of tube of inner diameter , of 150 mm and height over the highest point of the technological device of the production line including roof.
- the chimney 5 is not and must not be fitted with terminal burner.
- Fed mixture of hydrogen and air is exhausted to atmosphere, whereas released hydrogen rises upright and therefore may not accumulate to a phase of explosive mixture, i.e. 1 - 99 % H/0 2 .
- Exhausted hydrogen is not a substance causing greenhouse effect, is neither poisonous nor toxic and not explosive if diluted to high proportion. Environment is not exposed to smell, airborne particles etc.
- Direct output from the reactor 1 is fed to the chimney 5 through the safety valve (used for relieving of dangerous overpressure) and the collection pipeline K of the chimney 5 has terminated outputs from each device and tank in the hydrogen zone fitted with safety valves and they are used for exhaust of dangerous positive pressure.
- An important feature of the production process according to the invention is purification of the generated hydrogen.
- Hydrogen from the reactor I is fed to the washing tank 6. which is 70% filled with treated oxygen-free from the reservoir 13 of the emergency and service water. The remaining 30% of the volume of the washing tank 6 consists of washed hydrogen.
- Hydrogen is fed to the washing tank 6 through small holes to bubble across the water column. In this way, water steam as well as lye drops are removed.
- Water is added to the washing tank 6 from the reservoir 13. of emergency and service water. Certain part of the water used goes to the first precipitator 16 A1(QH) 3 .
- the washed hydrogen goes to separation of water to the separation, tank 8.
- the separation tank 8 is the tank 90% filled with Raschig rings where water from the washing tank 6 is precipitated and -ran down on the rings with subsequent draining to the reservoir 13 of the emergency and service water. Relativel dry hydrogen continues to low- pressure hydrogen tank 3.
- the low-pressure hydrogen tank 3 serves as temporary store for generated hydrogen and for separation of residual water with the use of freezing lamellas cooled down to temperature of - 20 °C. Freezing takes place with the use of the cooler 22.
- the lamellas must be defrosted regularly with the service water from the reservoir 35 of hot service water. Defrosted water is drained to the reservoir 13 of emergency and service water.
- Dried hydrogen is pumped from the low-pressure hydrogen tank 3; with the use of medium-pressure compressor 2 to the medium-pressure reservoir 24 of service hydrogen from where it is used as H 2 rinse for rinsing (filling and air-displacing) of the reservoirs in the hydrogen zone.
- Pressure in low-pressure hydrogen tank 3 must be lower than operating pressure. Water contents in the finished hydrogen should riot exceed 5 ppm.
- Excessive hydrogen from the low-pressure hydrogen tank 3 is fed via high-pressure compressor 21 to high-pressure hydrogen tank 9 where it is stored under pressure of 230 at. Hydrogen is distributed from the high-pressure hydrogen tank 9 in the filling and distributing point 10 of hydrogen.
- the high-pressure hydrogen tank 9 is also fitted with draining 6f residual condensed water drained to the reservoir 13 of the emergency and service water.
- the filling and distributing point 10 of the hydrogen may pose various methods of use and sale of purified product (depends on agreement with customers).
- hydrogen may be filled in pressure cylinders or after repeated pressure reduction it may be used for electricity production when hydrogen is fed to the engine 45 ' that drives the alternator 46 producing electric energy.
- reaction liquid is drained to the tank ⁇ . with solenoid that traps all particles that can be captured by magnet. It may particularly include iron with admixture of trace elements of other metals.
- Reaction liquid flows to the mechanical filter 12, which is the tank fitted with filters arranged in descending order frorn 1 ,000 ⁇ micrometres to 4 micrometres. This filtration removes all mechanical particles larger than; 4 micrometres.
- Pur-ified reaction liquid flows for processing in the first 16 Al(OH)3 precipitator.
- accessory reservoirs are important, particularly the reservoir 13 of emergency and service water mainly used as reservoir of the emergency water for uncontrolled, reaction of the reactor 1. It is furthermore used as reservoir for collection of all service treated and oxygen-free water as well as for preparation of the reprocessed reaction liquid.
- the reservoir 1_3 of the emergency and operation water is connected to the deaeration and saturation reservoir 14 used for deaeration of newly feeding treated water from the reservoir 23 of the cooling water and to subsequent saturation with service hydrogen (H 2 rinse). Water treated in this way is pumped to the reservoir 13 of emergency and service water with the use of the medium-pressure service hydrogen (1 1 2 rinse).
- Another accessory tank is the first reservoir 15. of hydrochloric acid, which is the tank for deaerated HC1 used partially for neutralization of the reaction liquid . in the first J_6 Al(OH) 3 precipitator.
- the suspension is then
- neutralizing unit 25 where full neutralization is performed.
- the reservoir 19 for reprocessing of the reaction .liquid is used for preparation of the reprocessed reaction liquid for further, use in the reactor i.
- 80% of partially neutralized reaction liquid from the inter-reservoir , 18 of the reaction liquid is combined with 20% of new lye from the first reservoir 20 of sodium hydroxide.
- The: reaction liquid treated in this way flows back to the reactor 1 remaining 20% of the reaction liquid flows to the neutralizing unit 25.
- the first reservoir 20 of sodium hydroxide is the reservoir for clean new 50% sodium hydroxide added to the reaction liquid with 20% vol. ; share.
- the lye is deaerated, saturated with hydrogen and it is added to the reservoir 9 for regeneration of the reaction liquid.
- zone without hydrogen is important for operation of the device according to the invention (depicted on figure 1 outside the hydrogen zone with dashed line).
- the first device in the zone without hydrogen is the reservoir of cooling water 23, which is a tank used as reservoir of cooling water for reactor as well as reservoir of treated service water.
- Water for the reservoir 23 is obtained from the water treatment plant 44 from water pipeline or from other source, then also from the recrystallizing unit 27 for NaCl or condensate is fed from the condenser 28.
- Water from the reservoir 23 of cooling water is fed to the reactor 1 , washing tank 6, deaeration and saturation reservoir 14, to the neutralizing unit 25 and to the reservoir 3_1 for washing of Al(OH) 3 as mentioned below.
- Vast majority of the devices arranged in the zone without hydrogen is used for purification of aluminium hydroxide and for refining of its properties for subsequent sale; in addition this device is used for production of sodium chloride and distribution of hot service water.
- the reaction liquid flowing from the inter-reservoir J_8 in the hydrogen zone is fed to the neutralizing unit 25 in the zone without hydrogen.
- condenser 28 cooled service water is drained to the "reservoir' of cooling water 23.
- the condenser 28 serves id condensation of water steams coming from the NaCl crystallizing linit 27.
- Condensed water is drained from the condenser 28 to the reservoir of cooling; afer 23. ' ⁇ '.-Vr
- NaCl dryer 34. the crystallized sodium chloride from the cry stallizin ⁇ unit 27, . is dried in the tubs, also , with the use of hot service water from , the reservoir 35 of that service water, and subsequently it is manually .transferred to NaCl store 38 NaCl for dispatch. Salt steams from, drying are drained to atmosphere. ⁇ ..;
- the second precipitator 29 A1(0H) 3 is a tank where aluminium hydroxide is from the filter 17 for removal of A1(0H) 3 in the hydrogen zone and from the first filter 26 Al(OH) in the zone without hydrogen
- the second filter 30 is also fitted with the filters of descending mesh size from 80 micrometres to 20 micrometres.
- the precipitated hydroxide is separated and then manually transferred to the reservoir 31 for washing of Al(OH) 3.
- Liquor is pumped for hydrogen treatment to the reservoir 42 for deaeration and saturation and lye saturation with hydrogen in the hydrogen zone.
- the filtered hydroxide from the second filter 30 is mixed with clean water from the reservoir of cooling water 23 and NaCl present in the suspension is dissolved under constant stirring. Then the suspension is let to sediment, flow off drains the salt solution to the third filter 32 Al(OH) 3j clean water is filled again and the sediment is mixed after NaCl presence analysis.
- the suspension is drained to the third filter 32 Al(OH) 3 .
- the third filter 32 6f aluminium hydroxide consists of the tank fitted with filters of 80 micrometres to 20 micrometres in descending order. In this tank, already clean and washed aluminium hydroxide is filtered and manually' transferred to drying in the dryer 39. the water phase is drained to the NaCl crystallizing ' unit 27.
- the aluminium hydroxide dryer 39 contains tub heated with service water from the hot service water reservoir 35.
- packing and distribution point 33 Al(OH) 3j water steams are exhausted to atmosphere.
- the packing and distribution point 33 consists of a hall for warehousing of dried aluminium hydroxide intended for sale in the form requested by customer.
- the zone without hydrogen contains accessory devices such as hot service water reservoir 35.
- This is the reservoir for hot water coming from cooling of the reactor L .Hot water is distributed to the operation,, excessive water may be then used for other purposes such as drying of wood etc.
- the second reservoir 36 of hydrochloric acid is the tank for 37% hydrochloric acid used for neutralization of lye in ' the first precipitator 16 Al(OH) 3j neutralizing unit 25 and the second precipitator 29 Al(OH) 3j and for refilling of the first reservoir 15 of hydrochloric acid in the hydrogen zone:
- the second reservoir 37 of sodium hydroxide is the reservoir used for storing of operation lye .(purchased) used for neutralization in the first precipitator 16 Al(OH) 3> neutralizing unit 25 and the second precipitator 29 Al(OH) 3> and for refilling of the first reservoir 20 of sodium hydroxide in the hydrogen zone.
- the method and device according to the invention can be used for the industrial production of hydrogen and other produpts from waste aluminium materials in various forms, whereas the hydrogen and other products are purified to a condition suitable for subsequent industrial use.
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- Chemical & Material Sciences (AREA)
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- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- Combustion & Propulsion (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Health & Medical Sciences (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
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Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CZ20100268A CZ302453B6 (cs) | 2010-04-07 | 2010-04-07 | Zpusob výroby vodíku a dalších produktu a zarízení k provádení tohoto zpusobu |
| PCT/CZ2011/000030 WO2011124189A2 (en) | 2010-04-07 | 2011-04-06 | Method for the production of hydrogen and other products and device for carrying out this method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2556017A2 true EP2556017A2 (en) | 2013-02-13 |
Family
ID=44041778
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP11728765A Withdrawn EP2556017A2 (en) | 2010-04-07 | 2011-04-06 | Method for the production of hydrogen and other products and device for carrying out this method |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP2556017A2 (cs) |
| CZ (1) | CZ302453B6 (cs) |
| WO (1) | WO2011124189A2 (cs) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013150527A1 (en) * | 2012-04-05 | 2013-10-10 | H Force Ltd | A system and method for efficient production of hydrogen |
| WO2014062833A1 (en) * | 2012-10-16 | 2014-04-24 | Helton Bill W | Hydrogen production catalysts and associated systems and methods |
| CZ2013749A3 (cs) | 2013-09-30 | 2015-03-25 | Mourek Lukáš | Způsob recyklace odpadního hliníku a zařízení k provádění tohoto způsobu |
| WO2015089778A1 (en) * | 2013-12-19 | 2015-06-25 | Honeywell International Inc. | Heat dissipation material and method of making the same |
| CN104192796B (zh) * | 2014-09-04 | 2016-01-27 | 桂林浩新科技服务有限公司 | 一种自搅拌制氢装置 |
| RU173853U1 (ru) * | 2016-10-28 | 2017-09-14 | Общество с ограниченной ответственностью "Технологии алюмоэнергетики" (ООО "Технологии алюмоэнергетики") | Установка для получения оксидов алюминия высокой чистоты |
| JP7056372B2 (ja) * | 2018-05-22 | 2022-04-19 | Jfeエンジニアリング株式会社 | 水素製造方法及び水素製造装置 |
| FR3103482B1 (fr) * | 2019-11-25 | 2022-07-22 | Nebula Tech | Procédé et installation pour produire de l’hydroxyde d’aluminium |
| CN115259187B (zh) * | 2022-07-25 | 2024-01-16 | 河津市炬华铝业有限公司 | 一种高比表面积大孔拟薄水铝石粉体及其制备方法 |
| GB202213860D0 (en) * | 2022-09-22 | 2022-11-09 | Net Zero Scient Ltd | Hydrogen production process |
| CN115725984B (zh) * | 2022-12-16 | 2024-11-29 | 江苏双良氢能源科技有限公司 | 一种镍基析氢催化剂的活化方法 |
| FR3148590A1 (fr) * | 2023-05-12 | 2024-11-15 | Novacium | Installation pour la production de h2 |
| ES2994603A1 (es) * | 2024-07-19 | 2025-01-27 | Benitez Salvador Luis Miguel | Dispositivo de valorizacion de envases flexibles de plastico o carton, rechazos de envases con contenido metalico mediante reaccion quimica |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3401194A1 (de) | 1984-01-14 | 1985-07-18 | Werner 7433 Dettingen Schweikert | Einrichtung zum nutzen der energie aus verschiedenen metallabfaellen in verbindung mit natronlauge |
| JPH01208301A (ja) * | 1988-02-15 | 1989-08-22 | Mitsubishi Heavy Ind Ltd | 水素発生方法 |
| DE4129328A1 (de) * | 1991-09-04 | 1993-03-11 | Solvay Werke Gmbh | Verfahren und vorrichtung zur herstellung von aluminiumhydroxychlorid und/oder -bromid und die verwendung in kosmetischen oder pharmazeutischen zubereitungen |
| US5286473A (en) * | 1993-02-01 | 1994-02-15 | Nobuyasu Hasebe | Process for the production of hydrogen |
| US6506360B1 (en) | 1999-07-28 | 2003-01-14 | Erling Reidar Andersen | Method for producing hydrogen |
| JP2003226502A (ja) * | 2002-02-06 | 2003-08-12 | Mitsubishi Heavy Ind Ltd | 水素発生装置及び方法 |
| CN100563820C (zh) | 2006-04-29 | 2009-12-02 | 刘欣 | 一种用铝从水中置换出氢气的催化剂 |
| AT504050A1 (de) | 2006-08-07 | 2008-02-15 | Alvatec Alkali Vacuum Technolo | Wasserstoffgenerator |
| KR100803074B1 (ko) * | 2007-03-20 | 2008-02-18 | 박정태 | 수소발생용 조성물 및 이를 이용한 고순도 수소발생 장치 |
| RU2356830C2 (ru) | 2007-06-26 | 2009-05-27 | ОАО Научно-производственное предприятие "Квант" | Способ получения водорода |
| US8323364B2 (en) * | 2007-07-31 | 2012-12-04 | Purdue Research Foundation | Control system for an on-demand gas generator |
| CN101284647B (zh) * | 2008-02-29 | 2011-05-11 | 邓振炎 | 表面改性铝粉体与水反应产生氢气的工艺方法 |
| CN101284646B (zh) * | 2008-02-29 | 2011-07-20 | 上海大学 | 用纯铝粉体与水反应产生氢气的工艺方法 |
| US20100061923A1 (en) * | 2008-09-05 | 2010-03-11 | Reddy Alla V K | Hydrogen production and use |
-
2010
- 2010-04-07 CZ CZ20100268A patent/CZ302453B6/cs not_active IP Right Cessation
-
2011
- 2011-04-06 WO PCT/CZ2011/000030 patent/WO2011124189A2/en not_active Ceased
- 2011-04-06 EP EP11728765A patent/EP2556017A2/en not_active Withdrawn
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2011124189A2 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CZ2010268A3 (cs) | 2011-05-25 |
| WO2011124189A4 (en) | 2012-04-19 |
| WO2011124189A2 (en) | 2011-10-13 |
| WO2011124189A3 (en) | 2012-02-23 |
| CZ302453B6 (cs) | 2011-05-25 |
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