CN105621658A - Sulfur transfer agent and FCC catalyst production fine-powder and wastewater utilization method - Google Patents
Sulfur transfer agent and FCC catalyst production fine-powder and wastewater utilization method Download PDFInfo
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Abstract
The invention discloses a sulfur transfer agent and FCC catalyst production fine-powder and wastewater utilization method. The method comprises the following steps: carrying out solid-liquid pre-separation treatment on FCC catalyst production wastewater so as to obtain pre-separated clear liquid and pre-separated heavy phase and/or sediment, carrying out levigation treatment on the pre-separated clear liquid and pre-separated heavy phase and/or sediment and sending the levigated substances into a gel-forming kettle for production of an FCC catalyst; mixing the pre-separated clear liquid and production wastewater of a sulfur transfer agent, adding fine powder of the sulfur transfer agent, controlling pH value, carrying out two-stage separation treatment, sending a separated clear liquid obtained to the sulfur transfer agent production process, and sending the levigated heavy phase and/or sediment into a gel-forming kettle for production of the sulfur transfer agent. According to the invention, fine powder of auxiliary agents and rare earth element and solid particles which are dissolved in wastewater can be reused. Thus, resources are recovered, and environmental pollution is reduced.
Description
Technical field
The present invention relates to a kind of sulfur transfer additive and the Application way of FCC catalyst production fine powder and waste water.
Background technology
In fluid catalytic cracking (FCC) process, raw oil and catalyst Rapid contact in riser carry out catalytic cracking reaction, the coke laydown that reaction generates causes it to inactivate to catalyst, and the catalyst of green coke inactivation enters regenerator after stripping and carries out coke burning regeneration. In regenerative process, it is deposited on the selective oxidation of sulfur containing compounds in particular in coke and generates SOx, be discharged in air with regenerated flue gas and cause environmental pollution.
Using flue gas SOx transferring assistant (also referred to as sulfur transferring assistant or sulfur transfer additive) is the technical measures controlling FCC apparatus regenerated flue gas SOx discharge. Its action principle is, the SOx by generating in metal active constituent trapping flue gas, forms stable metal sulfate, enter riser reactor with regenerator subsequently in a regenerator, and under reducing atmosphere, metal sulfate is reduced, with H2S form enters in gaseous product, sulfur recovery facility reclaim. Other flue gases SOx treatment technologies such as the relative wet scrubbing of sulfur transfer additive have flexible operation simplicity, do not need plant modification and equipment investment and do not produce the advantages such as secondary pollution, obtain common concern and application in refinery. Therefore, sulfur transfer additive has become the auxiliary agent kind that catalyst plant is important.
The chemical composition of sulfur transfer additive and FCC catalyst have significant difference, and sulfur transfer additive composition disclosed in prior art and preparation method thereof can referring to US4497902, US4768235, CN1485132A, CN100425339C, CN101185829A etc. Such as, sulfur transfer additive disclosed in CN1485132A is with the oxide of the cerium of 2-30 weight % for active component, with 70-98 weight % containing magnesium aluminate spinel compositions for carrier, described containing in magnesium aluminate spinel compositions possibly together with the V of 0-15 weight %, the rare earth element in addition to Ce of preferred 0.5-10 weight % and 0-10 weight %, preferred 0.5-5 weight %2O5. Rare earth element is CeO especially2Being the important active component of sulfur transfer additive, the dipping method (excessive dipping) adopting impregnation liquid volume excessive is carried on carrier, and the saturated dipping method of relative equal-volume can improve CeO2Scattered uniformity, improves the sulfur transfer efficiency of auxiliary agent. But the method for excessive dipping can produce a large amount of filtrate waste water, the method provided by CN1485132A, CN100425339C produces sulfur transfer additive, the method of the rare earth element ce excessive dipping of employing loads in the microspheroidal support after spray-dried shaping and roasting, owing to Ce is generally not capable of the absorption of complete loaded body, the Ce not being fully utilized, with filtrate discharge, causes CeO in filtrate waste water2Content may be up to 20 g/l sometimes. Additionally, in filter process, a small amount of builder granule particularly some fine graineds can pass through filter cloth and enter in waste water, also result in the solid particulate matter containing 5-25 g/l in waste water, thus waste water is in appearance in the dense thick suspension of mud color.
Because sulfur transfer additive contains the metal component of multiple easy pollution FCC catalyst, it produces waste water and can not be back to use in FCC catalyst production. Even if by self production procedure of waste water recycling to sulfur transfer additive, if not treated direct-on-line recycles, there is also problems with: (1) is if being back to preparation rare earth impregnation liquid, the fine particle and the rare earth flocculation sediment that then wherein contain constantly are accumulated, causing filter cloth mesh to block gradually, filter efficiency is greatly reduced; (2) if being back to use in plastic process, then when colloid spraying shapes, contained solid particulate matter not only easy abrasion spray drying tower atomizer, and causes builder granule sphericity poor with colloid adhesion, affects abrasion resistance properties. Owing to recycling existing problems online, thus sulfur transfer additive production process needs outer row containing the waste water of rare earth and builder granule thing, not only cause resources loss, and after mixing with other waste water, cause sewage disposal difficulty to increase, be easily caused problem of environmental pollution.
Although sulfur transferring assistant produces waste water and needs special concern because of reasons such as its rare earth element and fine particle content height, but is actually that oil refining catalyst factory produces the part in waste water in a large number. As known in this area research worker, FCC catalyst is the topmost catalizer variety of oil refining catalyst factory, the substantial amounts of exchange washing water of same generation and other sewage in FCC catalyst produces. Wherein, the exchange washing water consumption washed in sodium process for catalyst exchange is maximum, through filtering and producing a large amount of filtrate after catalyst solid-liquid separation. These filtrate waste water is in acidity, except containing sodium ion, ammonia nitrogen and solid particle beyond the region of objective existence, possibly together with the rare earth element run off from catalyst, although its concentration is relatively low, but owing to washings consumption is relatively big, thus higher with filtrate loss rare earth resources total amount. Due in washings dissolved with the sodium ion to the toxic effect of FCC catalyst, it is impossible to circulating and recovering in Cracking catalyst produce in. For reducing the consumption of water in Catalyst Production, reducing sewage discharge, in prior art, the methods adopting filtrate waste water segmentation reuse step by step, produce or catalyst cake drip washing for molecular sieve more. But owing to filtrate waste water containing sodium ion, rare earth ion, solid particulate matter and other impurity etc., reuse process is likely to molecular sieve and catalyst prod quality are caused certain impact. Therefore, if having new process and utilizing technology can tap portion filtrate waste water, then can reduce on the one hand outside waste water and arrange, on the other hand, molecular sieve and in Catalyst Production the usage ratio of fresh water be improved, be conducive to stabilized product quality.
In addition, in sulfur transfer additive production process, similar with conventional FCC catalyst production process, generating section fine powder in spray-drying process, these fine powders are easily less easily entrained by effusion and cause loss of material or granular material discharged pollution, so that the different phase in production procedure adopts the modes such as cyclone separator to reclaim. Fired before fine powder can be back to use in colloid generating kettle again making beating dispersion or return in roaster charging, but there is some problems in the fine powder reuse after roaster, if being back to use in plastic process, the then solid particulate matter in above-mentioned waste water, can adversely affect spray drying tower atomizer and auxiliary agent sphericity and abrasion resistance properties; Directly it is blended in catalyst or Additives Products, is then likely to result in product fine powder content beyond quality index requirement.
Above-mentioned prior art (US4497902, US4768235, CN1485132A, CN100425339C, CN101185829A) although in the composition disclosing multiple different sulfur transfer additive and preparation method thereof, but it is not directed to auxiliary agent fine powder and produces the reuse problem of waste water, the problem being especially not directed to simultaneously process to realize recycling online to auxiliary agent fine powder and waste water.
CN203392959U discloses the segregation apparatus of dead catalyst in a kind of flue gas desulfurization waste-water, mainly for separating of the dead catalyst in FCC regenerated flue gas wet scrubbing device waste water. Waste water enters cyclone hydraulic separators, and the thin liquid that top catalyst content is low is recycled back into chilling tower, is easily separated rich in the material of catalyst granules and the laggard dewaterer of flocculant mix and blend after bottom is concentrated. This segregation apparatus is mainly used in the spent catalyst particles in elimination regenerated flue gas wet scrubbing device, the production process of sewage, component characteristic and sulfur transfer additive and FCC catalyst production waste water significant difference. And solid-liquid separation efficiency is not high enough, needs the materials such as additional flocculating agents.
CN100429157C discloses during a kind of oil refining catalyst produces the high-concentration ammonia nitrogen waste water treatment method produced, and key step includes regulating pH value of waste water, removes sial ion and the compound thereof of the float in waste water and dissolving through solid-liquid separation; Add calcium ion and generate calcium sulfate precipitation, reduce the acidic materials in waste water through solid-liquid separation; Add carbanion and generate precipitation of calcium carbonate, remove the calcium ion in waste water through solid-liquid separation; Then through stripping deamination and biochemical treatment, waste water is made to reach discharging standards. The goal of the invention of the method is in that, combines to catalyst production waste water purified treatment by methods such as chemical precipitation and stripping ammonia nitrogen removals, makes discharged wastewater met the national standard. But described processing method primarily focuses on the aspect such as removal of ammonia and nitrogen, suspended particulate substance, need the material such as additional flocculating agents, chemical precipitation agent, operate relative complex, and do not consider the reuse of contained rare earth resources.
Currently, along with the requirement of the aspects such as catalyst plant stabilized product quality, energy-saving and emission-reduction is improved constantly, enterprise is in the urgent need to improving the process producing fine powder and waste water further and utilizing technical merit, thus is necessary the recycle utilization developing more effective sulfur transfer additive and FCC catalyst production fine powder and waste water.
Summary of the invention
It is an object of the invention to provide a kind of sulfur transfer additive and the Application way of FCC catalyst production fine powder and waste water, the method is by adopting containing wastewater from catalyst pre-separation, auxiliary agent fine powder to the pretreatment of composite waste, two-stage solid-liquid separation and the levigate process separating heavy phase and/or sediment, fine powder and rare earth element and solid particulate matter with discharging in waste water can be back to use in production procedure online, and product quality and production procedure adversely not affected.
To achieve these goals, the present invention provides a kind of sulfur transfer additive and FCC catalyst to produce the Application way of fine powder and waste water, the method includes: FCC catalyst first produces waste water and carries out solid-liquid pre-separation process, obtains pre-separation clear liquid and the pre-separation heavy phase containing solid particulate matter and/or sediment; Described pre-separation heavy phase and/or sediment being carried out levigate process, obtains the levigate process heavy phase of pre-separation and/or sediment, in process heavy phase that described pre-separation is levigate and/or sediment, the mean diameter of solid particulate matter is less than 4.5 microns; Levigate for described pre-separation process heavy phase and/or sediment are delivered to reuse in FCC catalyst colloid generating kettle; By volume, the sulfur transfer additive of 1 part is produced waste water and mixes with the described pre-separation clear liquid of 0.2-5 part, obtain sulfur transfer additive and FCC catalyst mixture manufacturing waste water; Using sulfur transfer additive fine powder as helping sedimentation agent to join in described mixture manufacturing waste water, obtain mixing suspension; With the volume of described mixture manufacturing waste water for benchmark, the addition of described sulfur transfer additive fine powder is 1-15 g/l; The pH value of described mixing suspension is controlled at 2-6; The mixing suspension that this pH value is 2-6 is carried out one-level solid-liquid separation process, obtains one-level clear liquid and the one-level heavy phase containing solid particulate matter and/or sediment; Described one-level clear liquid carries out two grades of solid-liquid separation process, obtain two grades of clear liquids and two grades of heavy phases containing solid particulate matter and/or sediment; Then more described two grades of clear liquids are transported in the production process of sulfur transfer additive and are circulated utilization, levigate process is carried out after described two grades of heavy phases and/or sediment being mixed with described one-level heavy phase and/or sediment, obtaining the levigate process heavy phase of sulfur transfer additive and/or sediment, in process heavy phase that described sulfur transfer additive is levigate and/or sediment, the mean diameter of solid particulate matter is less than 4.5 microns; Levigate for described sulfur transfer additive process heavy phase and/or sediment are delivered to reuse in the auxiliary agent colloid generating kettle in sulfur transfer additive production process.
Preferably, wherein, it is 3.5-5 that described FCC catalyst produces the pH value of waste water, containing the rare earth element in oxide weight 0.2-1.5 g/l, with the solid particulate matter of dry basis 0.5-10 g/l; Wherein, in oxide weight, described FCC catalyst produces the content of Ce in waste water and is not less than the 20% of whole rare earth element content.
Preferably, wherein, it is 5-8 that described sulfur transfer additive produces the pH value of waste water, containing the rare earth element in oxide weight 1-20 g/l, with the solid particulate matter of dry basis 2-25 g/l.
Preferably, wherein, described sulfur transfer additive fine powder is the fine powder produced in sulfur transfer additive production process, and the mean diameter of this fine powder is 2-20 micron.
Preferably, wherein, first described sulfur transfer additive fine powder is re-used as after 0.5-4 hour 450-800 DEG C of roasting and helps sedimentation agent to join in described sulfur transfer additive and FCC catalyst mixture manufacturing waste water.
Preferably, wherein, the pH value of described mixing suspension controls at 3-5.
Preferably, wherein, the pH value of described mixing suspension is controlled by adding hydrochloric acid.
Preferably, wherein, by using subsider, filter or cyclone hydraulic separators to carry out described solid-liquid pre-separation process and/or the process of one-level solid-liquid separation.
Preferably, wherein, by using centrifugal separator to carry out described two grades of solid-liquid separation process.
Preferably, wherein, described two grades of clear liquids are transported in the rare earth material-compound tank in sulfur transfer additive production process, auxiliary agent colloid generating kettle and/or carrier impregnation tank it are circulated utilization.
Preferably, wherein, first in described pre-separation heavy phase and/or sediment, add at least one in described FCC catalyst fine powder, molecular sieve, aluminium oxide and Kaolin, obtain pre-separation mixing heavy phase and/or sediment; Described pre-separation being mixed heavy phase and/or sediment carries out levigate process, obtain levigate process of pre-separation and mix heavy phase and/or sediment, in process mixing heavy phase that described pre-separation is levigate and/or sediment, the mean diameter of solid particulate matter is less than 4.5 microns; Levigate for described pre-separation process mixing heavy phase and/or sediment are delivered to reuse in FCC catalyst colloid generating kettle; Wherein, with dry basis, the weight of described pre-separation heavy phase and/or sediment is 0.1��10 times of weight at least one in described FCC catalyst fine powder, molecular sieve, aluminium oxide and Kaolin.
Preferably, wherein, after described two grades of heavy phases and/or sediment being mixed with described one-level heavy phase and/or sediment, add sulfur transfer additive fine powder and/or aluminium oxide, obtain sulfur transfer additive mixing heavy phase and/or sediment; Then sulfur transfer additive mixing heavy phase and/or after sediment carries out levigate process, obtain that sulfur transfer additive is levigate processes mixing heavy phase and/or sediment, described sulfur transfer additive is levigate processes in mixing heavy phase and/or sediment the mean diameter of solid particulate matter less than 4.5 microns; Levigate for described sulfur transfer additive process mixing heavy phase and/or sediment are delivered to reuse in sulfur transfer additive colloid generating kettle; Wherein, with dry basis, the gross weight of described two grades of heavy phases and/or sediment and described one-level heavy phase and/or sediment is 0.1��10 times of described sulfur transfer additive fine powder and/or alumina weight.
Preferably, wherein, adopting at least one levigate process device in cutter, ball mill and sand mill to carry out described levigate process, the time of levigate process is 5-60 minute.
Preferably, wherein, described FCC catalyst fine powder is the fine powder produced in FCC catalyst production process, and the mean diameter of this fine powder is 2-20 micron.
Sulfur transfer additive provided by the invention and FCC catalyst produce the Application way of fine powder and waste water, FCC catalyst produces waste water after solid-liquid pre-separation, produce waste water with sulfur transfer additive to mix, before composite waste is easily separated process, adopt the fine powder produced in sulfur transfer additive preparation as helping sedimentation agent that waste water is carried out pretreatment, described being used as helps the auxiliary agent fine powder of sedimentation agent to add front fired process in waste water, pH is controlled in conjunction with adding acid, waste water solid separating difficulty can be significantly reduced, subsequently by the fine particle in two-stage solid-liquid separation efficient removal waste water, the online recycling realizing waste water rare earth elements utilizes. containing substantial amounts of alkaline-earth metal and heavy metal in forming due to sulfur transfer additive, thus, FCC catalyst produces the sodium ion in waste water and is back to during sulfur transfer additive produces and will not the serviceability of sulfur transfer additive be adversely affected. pre-separation heavy phase that catalyst production waste water pre-separation obtains and/or sediment, can add other catalyst fines, after levigate process, be transported to FCC catalyst colloid generating kettle reuse. the separation heavy phase based on solid particulate matter that composite waste obtains through two-stage solid-liquid separation and/or sediment, can add other auxiliary agent fine powder, after levigate process, be transported to auxiliary agent colloid generating kettle reuse. product quality and production procedure particularly filter filter efficiency are not adversely affected by described wastewater recycling method.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, is used for explaining the present invention, but is not intended that limitation of the present invention together with detailed description below. In the accompanying drawings:
Fig. 1 is the schematic flow sheet of the circulation utilization method producing waste water according to the sulfur transfer additive of a kind of detailed description of the invention of the present invention.
Detailed description of the invention
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail. It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention.
The present invention provides a kind of sulfur transfer additive and FCC catalyst to produce the Application way of fine powder and waste water, the method includes: FCC catalyst first produces waste water and carries out solid-liquid pre-separation process, obtains pre-separation clear liquid and the pre-separation heavy phase containing solid particulate matter and/or sediment; Described pre-separation heavy phase and/or sediment being carried out levigate process, obtains the levigate process heavy phase of pre-separation and/or sediment, in process heavy phase that described pre-separation is levigate and/or sediment, the mean diameter of solid particulate matter is less than 4.5 microns; Levigate for described pre-separation process heavy phase and/or sediment are delivered to reuse in FCC catalyst colloid generating kettle; By volume, the sulfur transfer additive of 1 part is produced waste water and mixes with the described pre-separation clear liquid of 0.2-5 part, obtain sulfur transfer additive and FCC catalyst mixture manufacturing waste water; Using sulfur transfer additive fine powder as helping sedimentation agent to join in described mixture manufacturing waste water, obtain mixing suspension; With the volume of described mixture manufacturing waste water for benchmark, the addition of described sulfur transfer additive fine powder is 1-15 g/l; The pH value of described mixing suspension is controlled at 2-6; The mixing suspension that this pH value is 2-6 is carried out one-level solid-liquid separation process, obtains one-level clear liquid and the one-level heavy phase containing solid particulate matter and/or sediment; Described one-level clear liquid carries out two grades of solid-liquid separation process, obtain two grades of clear liquids and two grades of heavy phases containing solid particulate matter and/or sediment; Then more described two grades of clear liquids are transported in the production process of sulfur transfer additive and are circulated utilization, levigate process is carried out after described two grades of heavy phases and/or sediment being mixed with described one-level heavy phase and/or sediment, obtaining the levigate process heavy phase of sulfur transfer additive and/or sediment, in process heavy phase that described sulfur transfer additive is levigate and/or sediment, the mean diameter of solid particulate matter is less than 4.5 microns; Levigate for described sulfur transfer additive process heavy phase and/or sediment are delivered to reuse in the auxiliary agent colloid generating kettle in sulfur transfer additive production process.
FCC catalyst of the present invention production waste water can come from the FCC catalyst exchange washing serosity in FCC catalyst production process through filtering a part for filtrate or the filtrate produced, can be from waste water produced by other process that FCC catalyst produces, this is well known to those skilled in the art. Wherein, it can be 3.5-5 that described FCC catalyst produces the pH value of waste water, with oxide (RE2O3) total content of rare earth element of weighing scale can be 0.2-1.5 g/l, can for 0.5-10 g/l with the content of the solid particulate matter of dry basis, the mean diameter of solid particulate matter can be 3-8 microns, with oxide (RE2O3) weighing scale, described FCC catalyst produces the content of Ce in waste water and is not less than the 20% of whole rare earth element content. Described waste water can also contain the zwitterions such as sodium ion, ammonium radical ion, chloride ion.
The preparation method of sulfur transfer additive be usually first using as carrier material containing magnesium hydroxide, magnesium oxide, aluminium oxide, clay etc. in colloid generating kettle after plastic by carrier microballoons granule that spray drying forming is similar to catalytic cracking catalyst, carrier microballoons granule is carried out calcination process, then by impregnating mainly including the active constituent loading of the rare earth elements such as cerium to carrier in impregnating autoclave, then it is dried. According to the present invention, it can be all waste water produced in sulfur transfer additive production process that described sulfur transfer additive produces waste water, for instance the waste water produced during dipping, wherein, the pH value of described waste water is approximately in about 5-8, typically contains with oxide (RE2O3) rare earth element of weighing scale 1-20 g/l, rare earth element in described waste water, such as Ce, can exist with ionic state, can also exist with precipitate state, and also containing the solid particulate matter with dry basis 2-25 g/l, the mean diameter of described solid particulate matter, at 3-8 microns, has the composition same or like with sulfur transfer additive.
According to the present invention, by wastewater volume, the described pre-separation clear liquid mixed proportion that described sulfur transfer additive obtains after producing waste water and FCC catalyst producing waste water pre-separation process can be not less than 0.2:1, it is preferred to 0.2:1-5:1, more preferably 0.5:1-5:1.
According to the present invention it is possible to using sulfur transfer additive fine powder as helping sedimentation agent to join in sulfur transfer additive and FCC catalyst mixture manufacturing waste water, waste water is carried out pretreatment. Described sulfur transfer additive fine powder can come from the finished product collector unit of sulfur transfer additive production process, such as, can come from the fines collection unit of airstream drying tower, can be from the fine powder that spray drying tower place, finished product packing feed bin etc. collect, it is preferable that from the fine powder that airstream drying tower, finished product packing feed bin etc. are collected. The mean diameter of described sulfur transfer additive fine powder can at 2-20 microns, it is preferred to 5-15 microns. Described sulfur transfer additive fine powder first 450-800 DEG C of roasting 0.5-4 hour, can be re-used as after 1-2 hour more preferably in 550-750 DEG C of roasting and help sedimentation agent to join in sulfur transfer additive and FCC catalyst mixture manufacturing waste water. With the volume of described production waste water for benchmark, the addition of described sulfur transfer additive fine powder is 1-15 g/l, it is preferred to 2-10 g/l.
According to the present invention, in order to be conducive to follow-up solid-liquid separation, it is possible to the pH value of the mixing suspension obtained by the described mixture manufacturing waste water adding described sulfur transfer additive fine powder controls at 2-6, it is preferable that control at 3-5, acid used by control ph has no particular limits, it is preferred to use hydrochloric acid.
According to the present invention, it is well-known to those skilled in the art that described solid-liquid pre-separation process, firsts and seconds solid-liquid separation process the segregation apparatus used, for example, it is possible to by using subsider, filter or cyclone hydraulic separators to carry out described solid-liquid pretreatment separation and/or the process of one-level solid-liquid separation. Preferably, it is possible to carrying out described solid-liquid pre-separation by filter-press type filter and process, the pressure of described filter-press type filter is typically in 0.2-1.0MPa, it is preferable that 0.4-0.8MPa. Described one-level solid-liquid separation can be carried out by filter-press type filter or cyclone hydraulic separators to process, further, cyclone hydraulic separators is preferably used and carries out the process of described one-level solid-liquid separation, the inlet pressure of cyclone hydraulic separators is 0.1-0.5MPa, it is preferably 0.2-0.4MPa, underflow and overflow volume flow-rate ratio can control at 1:5-1:20, it is preferred to 1:8-1:15. Can by using centrifugal separator to carry out described two grades of solid-liquid separation process, described centrifugal separator is preferably high speed centrifuge, it is more preferably tubular-bowl centrifuge, the rotating speed of centrifuge particularly tube centrifuge can be 10000-50000rpm, being preferably 12000-20000rpm, described tube centrifuge can be separate unit or adopt multiple stage parallel operation. A kind of detailed description of the invention according to the present invention, carry out after one-level solid-liquid separation through cyclone hydraulic separators, overfall clear liquid can deliver into tubular type centrifugal separator mutually and carry out two grades of solid-liquid separation, remove fine particle further, the separation heavy phase of centrifuge and/or sediment can be discharged by slag-drip opening interval, clear liquid middle solid particulate matter mean concentration mutually is in general lower than 0.8g/L, it is preferable that lower than 0.2g/L, see the solution being substantially clarification in appearance.
It will be understood by those skilled in the art that, according to the present invention, can be undertaken the rare earth element in described two grades of clear liquids further reclaiming and enrichment, but, described two grades of clear liquids are preferably transported in the production process of sulfur transfer additive and recycle online by the present invention, not only convenient but also can reduce fresh water magnitude of recruitment and the rare earth inventory that sulfur transfer additive produces. The whereabouts recycled online includes, but are not limited to: be transported in rare earth material-compound tank, is used for preparing earth solution; It is back to use in auxiliary agent colloid generating kettle, pulls an oar for colloidal dispersions; Loop back the part as impregnation liquid in carrier impregnation tank; Wherein it is preferred that the part looped back in carrier impregnation tank as impregnation liquid.
According to the present invention, described FCC catalyst produces waste water and carries out pre-separation heavy phase and/or the sediment that solid-liquid pre-separation process obtains, after can mixing with FCC catalyst fine powder, carry out levigate process, reuse in the levigate colloid generating kettle processing mixing heavy phase and/or sediment feeding FCC catalyst production process of pre-separation obtained, by butt, mixing heavy phase and/or sediment for plastic account for the 1 of every still inventory butt gross weight and weigh %-20 weight %, it is preferred to 5 weight %-10 weight %. In process mixing heavy phase that pre-separation is levigate and/or sediment, the mean diameter of solid particulate matter is less than 4.5 microns, it is preferable that less than 3 microns. Described pre-separation heavy phase and/or sediment and affiliated catalyst fines press dry basis, and mixed proportion is 0.1-10:1, it is preferred to 0.5-5:1. Wherein, described FCC catalyst fine powder is the fine powder produced in FCC catalyst production process, can come from any fines collection unit of FCC catalyst production process, such as, can come from the fines collection unit of airstream drying tower, can be from the fine powder that spray drying tower place, roaster, finished product packing feed bin etc. collect, it is preferable that coming spray drying tower, fine powder from airstream drying tower etc. cyclone collection, the mean diameter of this fine powder can be 2-20 micron. Described catalyst fines can also be partly or totally replaced with at least one in molecular sieve, aluminium oxide and Kaolin.
A kind of detailed description of the invention according to the present invention, it is possible to first add at least one in described FCC catalyst fine powder, molecular sieve, aluminium oxide and Kaolin in described pre-separation heavy phase and/or sediment, obtains pre-separation mixing heavy phase and/or sediment; Described pre-separation is mixed heavy phase and/or sediment carries out levigate process, obtain levigate process of pre-separation and mix heavy phase and/or sediment, in process mixing heavy phase that described pre-separation is levigate and/or sediment, the mean diameter of solid particulate matter is less than 4.5 microns, it is preferable that less than 3 microns; Levigate for described pre-separation process mixing heavy phase and/or sediment can be delivered to reuse in FCC catalyst colloid generating kettle; Wherein, with dry basis, the weight of described pre-separation heavy phase and/or sediment can be 0.1-10 times of weight at least one in described FCC catalyst fine powder, molecular sieve, aluminium oxide and Kaolin.
According to the present invention, it will be understood by those skilled in the art that, levigate process can be carried out after described two grades of heavy phases and/or sediment and described one-level heavy phase and/or sediment mixing, obtain the levigate process heavy phase of sulfur transfer additive and/or sediment, in heavy phase that described sulfur transfer additive is levigate and/or sediment, the mean diameter of solid particulate matter is less than 4.5 microns, it is preferable that less than 3 microns; Then levigate for described sulfur transfer additive process heavy phase and/or sediment can be delivered in the colloid generating kettle that sulfur transfer additive produces and be circulated utilization, by butt, mixing heavy phase and/or sediment for plastic account for the 1 of every still inventory butt gross weight and weigh %-10 weight %, it is preferred to 4 weight %-8 weight %. Further, for the sulfur transfer additive fine powder collected by the finished product collector unit that Appropriate application sulfur transfer additive produces, it is possible to sulfur transfer additive fine powder is joined in the colloid generating kettle delivering to sulfur transfer additive production after described one-level heavy phase and/or sediment carry out levigate process together with in described two grades of heavy phases and/or sediment and be circulated utilization. Wherein, with dry basis, the weight ratio of the gross weight of described one-level heavy phase and/or sediment and described two grades of heavy phases and/or sediment and the described sulfur transfer additive fine powder of addition can be 1:10-10:1, it is preferably 1:5-5:1, described sulfur transfer additive fine powder can also be partly or totally replaced with aluminium oxide, it is preferable that replaces with boehmite.
A kind of detailed description of the invention according to the present invention, it is possible to add sulfur transfer additive fine powder and/or aluminium oxide with described one-level heavy phase and/or sediment after described two grades of heavy phases and/or sediment being mixed, obtains sulfur transfer additive mixing heavy phase and/or sediment; Then sulfur transfer additive can be mixed heavy phase and/or after sediment carries out levigate process, obtain levigate process of sulfur transfer additive and mix heavy phase and/or sediment, in process mixing heavy phase that described sulfur transfer additive is levigate and/or sediment, the mean diameter of solid particulate matter is less than 4.5 microns, it is preferable that less than 3 microns; Levigate for described sulfur transfer additive process mixing heavy phase and/or sediment can be delivered to reuse in the colloid generating kettle of sulfur transfer additive production process; Wherein, with dry basis, the gross weight of described two grades of heavy phases and/or sediment and described one-level heavy phase and/or sediment can be 0.1��10 times of described sulfur transfer additive fine powder and/or alumina weight.
According to the present invention, it will be understood by those skilled in the art that, the levigate process device of at least one in cutter, sand mill and ball mill can be adopted to carry out described levigate process, the levigate process time can be 5-60 minute, preferably employ ball mill and carry out levigate process, can also adopting other levigate processing method industrial, the present invention is restriction not. Wherein, it is well-known to those skilled in the art that described employing ball mill carries out levigate process, and the slurry solid content of levigate process can be 10%-40%, and the time of levigate process can be 5-60 minute.
Following by embodiment, the method for the present invention is described further, but the present invention is not limited to this. Described instrument and equipment if no special instructions, is in prior art routine instrument device, but not thereby limiting the invention.
In all embodiments and comparative example experiment, sulfur transfer additive production and wastewater treatment all carry out on the existing Conventional catalytic cracking Catalyst Plant of Sinopec catalyst company limited. Wherein, the sulfur transfer additive used produces on average consisting of of efflux wastewater: CeO2Content is 12.5g/L, and solid particulate matter content is 10.3g/L, and mean diameter is 5.65 ��m, and pH value of waste water is 6.5. Containing the rare earth element of 0.8 g/l in catalyst exchange wash filtrate waste water, the mean diameter of 5.5 g/l is at the solid particulate matter of 5.36 ��m, and the pH value of described waste water is 4.5. Under the basic operating mode that existing efflux wastewater operates, belt filter filtering rate is generally at 2.2-2.5m3/ h, cake moisture is at 33-38%. Sulfur transfer additive fine powder takes from airstream drying tower cyclone separator, mean diameter 10.2 ��m, and in the embodiment of the present invention, above-mentioned fine powder is directly added in waste water and is used as to help sedimentation agent, or is used as to help sedimentation agent in addition waste water after 650 DEG C of roasting 1.5h. For no longer carrying out calcination process with the auxiliary agent fine powder of heavy phase and/or sediment mixed grinding. FCC catalyst fine powder is from spray drying tower cyclone separator, and mean diameter is 11.5 ��m, does not carry out calcination process with before pressure filter pre-separation gained filtering residue mixed grinding. Sulfur transfer additive and FCC catalyst straight tube abrasion index all adopt RIPP29-90 method measure (Yang Cuiding, Gu Kanying, Wu Wenhui compile. Petrochemical Engineering Analysis method. Beijing: Science Press, 1990). The qualified index of sulfur transfer additive abrasion index is��4.5, and the qualified index of FCC catalyst straight tube abrasion index is��3.0. In waste water solid particulate matter mean diameter adopt nephelometry be measured (Zheng Bo etc. the research of Nephelometric Determination solids in suspension granule density, petroleum refining and chemical industry, 2011,41 (10): 78-81), the mean diameter of fine powder adopts laser particle size analyzer to be measured by ASTMD4464 method.
Embodiment 1
This example demonstrates that sulfur transferring assistant of the present invention and FCC catalyst produce the circulation utilization method of fine powder and composite waste.
Catalyst production waste water adopts pressure filter to carry out solid-liquid pre-separation, operates pressure 0.7MPa, and filtrate is discharged continuously, filtering residue interval discharging. By volume effusion meter, the mixed proportion that filter press filtrate produces waste water with sulfur transfer additive is 1:1.
Adding 4g sulfur transfer additive fine powder after 650 DEG C of roasting 1.5h in every liter of composite waste, stirring mixing, with salt acid for adjusting pH value to 4. Waste water suspension pumps into cyclone hydraulic separators, and inlet pressure is 0.35MPa, underflow and overflow volume flow-rate ratio 1:8. Overflow outlet clear liquid is transported to tube centrifuge entrance mutually, and centrifuge speed is 15000rpm, and solid phase sediment was removed once at interval of 1 hour, and clear liquid phase particle content is 0.15g/L.
Clear liquid is transported in carrier impregnation tank, for the excessive dip loading rare earth of sulfur transfer vector. Every reuse 1m3Clear liquid can while substituting equivalent fresh water, and reducing rare earth inventory is 6.65kg. After continuous reuse 8h, filtering rate substantially remains in 2.4m3/ h, cake moisture is 35.5%, suitable with under row's operation operating mode outside waste water before reuse. Show that waste water is back in carrier impregnation process after the method for the invention processes, realizing while rare earth element recycles online, do not produce to significantly affect to filter filter efficiency.
The containing wastewater from catalyst filter cake that pressure filter obtains mixes with the fine powder that it is possible to additionally incorporate by butt weight ratio 1:2 after drawing off, and enters ball mill grinding, and grinding solid content is 32%, and milling time is 25min, and solid particle mean diameter reaches 2.25 microns. Slurry after grinding is back in catalyst colloid generating kettle, and by dry basis, reuse slurry accounts for the 8% of every still material total amount. After continuous reuse 8h, finished catalyst straight tube abrasion index is 1.6.
After cyclone hydraulic separators heavy phase and tube centrifuge sludge collection, by dry basis, add and the auxiliary agent fine powder of solid identical weight (1:1) in heavy phase and sediment, enter ball mill grinding, grinding solid content is 35%, milling time is 30min, and after grinding, solid particle mean diameter reaches 2.48 microns. Slurry after grinding is transported in auxiliary agent colloid generating kettle reuse in batches. By dry basis, the inventory of reuse slurry accounts for the 5% of every still material butt total amount. After continuous reuse 8h, auxiliary agent finished-product straight pipe abrasion index is 3.3. Show the separating obtained solid particulate matter of waste water and fine powder mixture material, be back to plastic process after ground process, auxiliary agent abrasion resistance properties do not adversely affected.
Embodiment 2
This example demonstrates that sulfur transferring assistant of the present invention and FCC catalyst produce the circulation utilization method of fine powder and composite waste.
Catalyst production waste water adopts pressure filter to carry out solid-liquid pre-separation, operates pressure 0.7MPa, and filtrate is discharged continuously, filtering residue interval discharging. By volume effusion meter, the mixed proportion that filter press filtrate produces waste water with sulfur transfer additive is 1:1.
Adding the 4g sulfur transfer additive fine powder without calcination process in every liter of composite waste, stirring mixing, with salt acid for adjusting pH value to 4. Waste water suspension pumps into cyclone hydraulic separators, and inlet pressure is 0.35MPa, underflow and overflow volume flow-rate ratio 1:8. Overflow outlet clear liquid is transported to tube centrifuge entrance mutually, and centrifuge speed is 15000rpm, and solid phase sediment is removed once at interval of 50min, and clear liquid phase particle content is 0.55g/L.
Clear liquid is transported in carrier impregnation tank, for the excessive dip loading rare earth of sulfur transfer vector. Every reuse 1m3Clear liquid can while substituting equivalent fresh water, and reducing rare earth inventory is 6.65kg. After continuous reuse 8h, filtering rate substantially remains in 2.3m3/ h, cake moisture is 36.2%, suitable with under row's operation operating mode outside waste water before reuse. Show that waste water is back in carrier impregnation process after the method for the invention processes, realizing while rare earth element recycles online, filter filter efficiency and cake moisture can be made to substantially remain within the scope of nominal situation.
The containing wastewater from catalyst filter cake that pressure filter obtains mixes with the fine powder that it is possible to additionally incorporate by butt weight ratio 1:0.8 after drawing off, and enters ball mill grinding, and grinding solid content is 30%, and milling time is 20min, and solid particle mean diameter reaches 2.42 microns. Slurry after grinding is back in catalyst colloid generating kettle, and by dry basis, reuse slurry accounts for the 5% of every still material total amount. After continuous reuse 8h, finished catalyst straight tube abrasion index is 1.8.
After cyclone hydraulic separators heavy phase and tube centrifuge sludge collection, by dry basis, add and the auxiliary agent fine powder of solid identical weight (1:1.5) in heavy phase and sediment, enter ball mill grinding, grinding solid content is 35%, milling time is 30min, and after grinding, solid particle mean diameter reaches 2.75 microns. Slurry after grinding is transported in auxiliary agent colloid generating kettle reuse in batches. By dry basis, the inventory of reuse slurry accounts for the 5% of every still material butt total amount. After continuous reuse 8h, auxiliary agent finished-product straight pipe abrasion index is 3.6. Show the separating obtained solid particulate matter of waste water and fine powder mixture material, be back to plastic process after ground process, auxiliary agent abrasion resistance properties do not adversely affected.
Comparative example 1
This comparative example is for illustrating that the not treated direct reuse of composite waste is in the impact on production procedure of the sulfur transfer additive carrier impregnation process.
By volume effusion meter, it is 1:1 that sulfur transfer additive produces the mixed proportion of waste water and catalyst production waste water. Undressed waste water is delivered directly in carrier impregnation tank, for the excessive dip loading rare earth of sulfur transfer vector. Every reuse 1m3While the same alternative equivalent fresh water of clear liquid, reducing rare earth inventory is 6.65kg. After continuous reuse 8h, filtering rate is reduced to 1.7m3/ h, cake moisture brings up to 40.4%. Show the undressed waste water direct reuse containing rare earth element in carrier impregnation process, although equivalent fresh water can be substituted equally, reduce rare earth inventory, but produce to significantly affect to filter filter efficiency and cake moisture.
Comparative example 2
This comparative example is for illustrating the composite waste the clear liquid reuse after the two-stage solid-liquid separation impact on production procedure.
The heavy phase obtained because of solid-liquid separation at different levels and/or sediment, after blending with catalyst or auxiliary agent fine powder, as long as through sufficient levigate process, all can be back to use in FCC catalyst or sulfur transfer additive production procedure by proper proportion, without product abrasion index is caused obvious adverse effect. Thus fine powder and cycling utilization of wastewater process need that pays close attention to be still the separation clear liquid impact on filter efficiency.
With reference to method described in embodiment 1, catalyst production waste water carried out solid-liquid pre-separation, and mix producing waste water with sulfur transfer additive in the ratio of 1:1. But in composite waste, do not add sulfur transfer additive fine powder, do not carry out pH value adjustment yet. But composite waste is pumped directly into cyclone hydraulic separators, inlet pressure is 0.35MPa, underflow and overflow volume flow-rate ratio 1:8. Overflow outlet clear liquid is transported to tube centrifuge entrance mutually, and centrifuge speed is 15000rpm, and solid phase sediment was removed once at interval of 0.5 hour, and clear liquid phase particle content is 1.09g/L. Clear liquid is transported in carrier impregnation tank, for the excessive dip loading rare earth of sulfur transfer vector. Every reuse 1m3Clear liquid can while substituting equivalent fresh water, and reducing rare earth inventory is 6.65kg. After continuous reuse 8h, filtering rate is reduced to 2.1m3/ h, cake moisture is 38.5%. Relative embodiment 2, the centrifuge scarfing cinder cycle of comparative example 2 significantly shortens, and solid-liquid separation effect is deteriorated, although can substitute equivalent fresh water equally, reduces rare earth inventory, but filter filter efficiency and cake moisture are produced significantly impact.
Comparative example 3
This comparative example is for illustrating that the not treated direct reuse of fine powder and composite waste prepares the impact on product quality and production procedure in sulfur transfer additive colloid.
By volume effusion meter, it is 1:1 that sulfur transfer additive produces the mixed proportion of waste water and catalyst production waste water. In every liter of composite waste, add 5g sulfur transfer additive fine powder, be delivered directly in auxiliary agent colloid generating kettle, for sulfur transfer vector making beating plastic. By dry basis, in every still material, reuse material proportion is 4%. After continuous reuse 8h, filtering rate is reduced to 2.1m3/ h, cake moisture brings up to 38.5%, and auxiliary agent finished-product straight pipe abrasion index is 5.2. Show undressed fine powder and waste water direct reuse in plastic process, although rare earth and raw material inventory can be reduced, but filter filter efficiency, cake moisture and auxiliary agent abrasion resistance properties are produced significant adverse impact.
Claims (14)
1. sulfur transfer additive and FCC catalyst produce an Application way for fine powder and waste water, and the method includes: FCC catalyst first produces waste water and carries out solid-liquid pre-separation process, obtains pre-separation clear liquid and the pre-separation heavy phase containing solid particulate matter and/or sediment; Described pre-separation heavy phase and/or sediment being carried out levigate process, obtains the levigate process heavy phase of pre-separation and/or sediment, in process heavy phase that described pre-separation is levigate and/or sediment, the mean diameter of solid particulate matter is less than 4.5 microns; Levigate for described pre-separation process heavy phase and/or sediment are delivered to reuse in FCC catalyst colloid generating kettle; By volume, the sulfur transfer additive of 1 part is produced waste water and mixes with the described pre-separation clear liquid of 0.2-5 part, obtain sulfur transfer additive and FCC catalyst mixture manufacturing waste water; Using sulfur transfer additive fine powder as helping sedimentation agent to join in described mixture manufacturing waste water, obtain mixing suspension; With the volume of described mixture manufacturing waste water for benchmark, the addition of described sulfur transfer additive fine powder is 1-15 g/l; The pH value of described mixing suspension is controlled at 2-6; The mixing suspension that this pH value is 2-6 is carried out one-level solid-liquid separation process, obtains one-level clear liquid and the one-level heavy phase containing solid particulate matter and/or sediment; Described one-level clear liquid carries out two grades of solid-liquid separation process, obtain two grades of clear liquids and two grades of heavy phases containing solid particulate matter and/or sediment; Then more described two grades of clear liquids are transported in the production process of sulfur transfer additive and are circulated utilization, levigate process is carried out after described two grades of heavy phases and/or sediment being mixed with described one-level heavy phase and/or sediment, obtaining the levigate process heavy phase of sulfur transfer additive and/or sediment, in process heavy phase that described sulfur transfer additive is levigate and/or sediment, the mean diameter of solid particulate matter is less than 4.5 microns; Levigate for described sulfur transfer additive process heavy phase and/or sediment are delivered to reuse in the auxiliary agent colloid generating kettle in sulfur transfer additive production process.
2. method according to claim 1, wherein, it is 3.5-5 that described FCC catalyst produces the pH value of waste water, containing the rare earth element in oxide weight 0.2-1.5 g/l, with the solid particulate matter of dry basis 0.5-10 g/l; Wherein, in oxide weight, described FCC catalyst produces the content of Ce in waste water and is not less than the 20% of whole rare earth element content.
3. method according to claim 1, wherein, it is 5-8 that described sulfur transfer additive produces the pH value of waste water, containing the rare earth element in oxide weight 1-20 g/l, with the solid particulate matter of dry basis 2-25 g/l.
4. method according to claim 1, wherein, described sulfur transfer additive fine powder is the fine powder produced in sulfur transfer additive production process, and the mean diameter of this fine powder is 2-20 micron.
5. method according to claim 1, wherein, is first re-used as described sulfur transfer additive fine powder after 0.5-4 hour 450-800 DEG C of roasting and helps sedimentation agent to join in described sulfur transfer additive and FCC catalyst mixture manufacturing waste water.
6. method according to claim 1, wherein, the pH value of described mixing suspension controls at 3-5.
7. method according to claim 1, wherein, controls the pH value of described mixing suspension by adding hydrochloric acid.
8. method according to claim 1, wherein, by using subsider, filter or cyclone hydraulic separators to carry out described solid-liquid pre-separation process and/or the process of one-level solid-liquid separation.
9. the method according to claim 1 or 8, wherein, processes by using centrifugal separator to carry out described two grades of solid-liquid separation.
10. described two grades of clear liquids wherein, are transported in the rare earth material-compound tank in sulfur transfer additive production process, auxiliary agent colloid generating kettle and/or carrier impregnation tank and are circulated utilization by method according to claim 1.
11. method according to claim 1, wherein, first in described pre-separation heavy phase and/or sediment, add at least one in described FCC catalyst fine powder, molecular sieve, aluminium oxide and Kaolin, obtain pre-separation mixing heavy phase and/or sediment; Described pre-separation being mixed heavy phase and/or sediment carries out levigate process, obtain levigate process of pre-separation and mix heavy phase and/or sediment, in process mixing heavy phase that described pre-separation is levigate and/or sediment, the mean diameter of solid particulate matter is less than 4.5 microns; Levigate for described pre-separation process mixing heavy phase and/or sediment are delivered to reuse in FCC catalyst colloid generating kettle; Wherein, with dry basis, the weight of described pre-separation heavy phase and/or sediment is 0.1��10 times of weight at least one in described FCC catalyst fine powder, molecular sieve, aluminium oxide and Kaolin.
12. method according to claim 1, wherein, after described two grades of heavy phases and/or sediment being mixed with described one-level heavy phase and/or sediment, add sulfur transfer additive fine powder and/or aluminium oxide, obtain sulfur transfer additive mixing heavy phase and/or sediment; Then sulfur transfer additive mixing heavy phase and/or after sediment carries out levigate process, obtain that sulfur transfer additive is levigate processes mixing heavy phase and/or sediment, described sulfur transfer additive is levigate processes in mixing heavy phase and/or sediment the mean diameter of solid particulate matter less than 4.5 microns; Levigate for described sulfur transfer additive process mixing heavy phase and/or sediment are delivered to reuse in sulfur transfer additive colloid generating kettle; Wherein, with dry basis, the gross weight of described two grades of heavy phases and/or sediment and described one-level heavy phase and/or sediment is 0.1��10 times of described sulfur transfer additive fine powder and/or alumina weight.
13. the method according to claim 1,11 or 12, wherein, adopting at least one levigate process device in cutter, ball mill and sand mill to carry out described levigate process, the time of levigate process is 5-60 minute.
14. method according to claim 11, wherein, described FCC catalyst fine powder is the fine powder produced in FCC catalyst production process, and the mean diameter of this fine powder is 2-20 micron.
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