CN107285366A - The technique that sodium sulfate waste liquid produces nano barium sulfate in a kind of utilization viscose rayon production - Google Patents
The technique that sodium sulfate waste liquid produces nano barium sulfate in a kind of utilization viscose rayon production Download PDFInfo
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- CN107285366A CN107285366A CN201610205155.8A CN201610205155A CN107285366A CN 107285366 A CN107285366 A CN 107285366A CN 201610205155 A CN201610205155 A CN 201610205155A CN 107285366 A CN107285366 A CN 107285366A
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- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
- C01F11/462—Sulfates of Sr or Ba
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The present invention relates to the technique that sodium sulfate waste liquid in a kind of production of utilization viscose rayon produces nano barium sulfate, the Abfallwirtschaft technical field belonged in viscose rayon production.The present invention includes pretreatment of raw material, metering and reaction and subsequent processing steps.The characteristics of sodium sulfate waste liquid that the present invention is produced in being produced for viscose rayon, using specific pretreatment and the method for subsequent treatment, with reference to micro passage reaction, sodium sulfate waste liquid produces the high nano-barium sulfate powder material of uniform particle, good dispersion, product quality in being produced using viscose rayon, so that refuse reclamation, increase benefit, reduce the pollution of environment.
Description
Technical field
The present invention relates to the handling process of waste liquid in a kind of production of viscose rayon, it is more particularly related to sodium sulfate waste liquid produces the technique of nano barium sulfate in a kind of production of utilization viscose rayon, the Abfallwirtschaft technical field belonged in viscose rayon production.
Background technology
In viscose glue production process in addition to the viscose rayon for producing high-quality, the generation of sodium sulfate byproduct is accompanied by.Production 1t viscose rayons can be along with 1t sodium sulphate be produced according to statistics, and substantial amounts of solid waste sodium sulphate can not be effectively addressed, not only cause larger economic loss, also result in huge environmental protection pressure.After after new environmental law regulation, many viscose glue enterprises cause the shut-down of many enterprises, stopped production because " three wastes " can not be handled effectively, cause great economic loss, therefore the waste residue effectively in processing " three wastes ", it has also become Business survival and the key of development.
Current most domestic is all that viscose glue is produced to the discarded object produced to be burnt and filled, and the result so caused is the shortcomings of carrying capacity of environment is big, water and soil pollution is big.With reference to intrinsic advantage, successively explore and sodium sulphate is electrolysed relieving haperacidity, sodium sulphate recombination reaction prepares industrial potash fertilizer, cost is excessive and face failure., can also co-producing sodium chloride and the preferable processing method of sodium sulfate byproduct is to generate barium sulfate or calcium sulfate with barium chloride or calcium chloride reaction.
State Intellectual Property Office discloses a Publication No. CN101792168A in 2010.8.4, the invention of entitled " a kind of method for preparing barium sulfate and co-producing sodium chloride ", a kind of method for preparing barium sulfate and co-producing sodium chloride of the disclosure of the invention, the industrial products of the industrial products of chloride containing barium and sulfur acid sodium are chemically reacted according to barium chloride and sodium sulphate pure material mass ratio 1: 0.38 ~ 0.66, the mixture of barium sulfate precipitate and sodium chloride solution is obtained；Mixture filters to obtain barium sulfate filter cake and sodium chloride filtrate；Barium sulfate filter cake is scrubbed, dry, pulverize, and is packaged to be barium sulfate product；Sodium chloride filtrate obtains sodium chloride product through vacuum distillation.It is simple and direct and lucid and lively that this method prepares barium sulfate, particularly with industrial goods barium chloride and sodium sulphate production barium sulfate, and production technology and equipments are simple, and greatly, profit is very high for yield.
State Intellectual Property Office discloses a Publication No. CN103159248A in 2013.6.19, the invention of entitled " a kind of production method of nanometer barium sulfate grains ", a kind of production method of nanometer barium sulfate grains of the disclosure of the invention, comprises the following steps：To concentration to add EDETATE DISODIUM in 0.01-0.3mol/L barium chloride solution, the mol ratio for making Chlorine in Solution barium and EDETATE DISODIUM is 1：1, didecyl Dimethy ammonium bromide is added, the molar concentration of didecyl Dimethy ammonium bromide is the 0.1-0.5% of barium chloride molar concentration, obtains solution one；Didecyl Dimethy ammonium bromide is added into molar concentration and barium chloride solution identical aqueous sodium persulfate solution, the molar concentration of didecyl Dimethy ammonium bromide in the solution is the 0.1-0.5% of sodium sulphate molar concentration, obtains solution two；Solution one and two is connect into microreactor entrance respectively, reaction product is filtered, washed, the filtrate drying after washing is obtained to the powdered granule of nano barium sulfate.Present invention microreactor suppresses barium sulfate precipitate under conditions of complexing agent presence, using surfactant and grown up, and it is tiny to obtain particle diameter, and the controllable nanometer barium sulfate grains of particle diameter.
State Intellectual Property Office discloses a Publication No. CN101423239 in 2009.5.6, the invention of entitled " a kind of controllable method for preparing nano barium sulfate of particle diameter distribution ", a kind of disclosure of the invention preparation method of the controllable nano barium sulfate of particle diameter distribution.The present invention is with BaCl2And Na2SO4For raw material, two kinds of solution are configured to respectively, are then added simultaneously with identical flow in the rotating liquid-film reactor of rotation at a high speed, are carried out into nuclear reaction, gained slurries pass through centrifuge washing and drying, obtain particle diameter for 30-120nm and the narrower nanometer BaSO of particle diameter distribution4.The operating parameters such as rotating speed, gap by adjusting control reactor, can reach the purpose of accurate control particle size, can prepare the BaSO that particle diameter is 30-40nm4.This method combines the advantage of microreactor and supergravity reactor, while the shortcomings of avoiding microemulsion method, complexometry, reaction compartment is small, prepares speed soon, can meet preparation of industrialization nanometer BaSO4Requirement.
Above-mentioned technical scheme of the prior art, which is disclosed using sodium sulphate and barium chloride as raw material, prepares nano barium sulfate, but these technical schemes are not carried out for sodium sulfate waste liquid in viscose rayon production, it is impossible to obtain the high nano-barium sulfate powder material of uniform particle, good dispersion, product quality.
The content of the invention
Present invention seek to address that the problem of prior art can not produce uniform particle, good dispersion, product quality high nano-barium sulfate powder material using sodium sulfate waste liquid in viscose rayon production, the technique that sodium sulfate waste liquid in a kind of utilization viscose rayon production produces nano barium sulfate is provided, sodium sulfate waste liquid produces the high nano-barium sulfate powder material of uniform particle, good dispersion, product quality in being produced using the technique using viscose rayon.
In order to realize foregoing invention purpose, its specific technical scheme is as follows：
The technique that sodium sulfate waste liquid produces nano barium sulfate in a kind of utilization viscose rayon production, it is characterised in that：Comprise the following steps that：
A, pretreatment of raw material
Sodium sulfate waste liquid and barium chloride solution are respectively by flocculation, sedimentation during viscose rayon is produced, and the supernatant of two kinds of raw materials finally carries out smart filtering using membrane filtration again respectively through coarse filtration, obtains pretreatment metabisulfite solution and pre-process barium chloride solution；
B, metering and reaction
Step A is pre-processed into obtained metabisulfite solution and barium chloride solution by measuring pump-metered, micro passage reaction is squeezed into, prepares nano barium sulfate slurry；
C, subsequent treatment
The obtained nano barium sulfate slurries of step B are added to blood separation sedimentator, add water wash cycles, until obtaining the nano-barium sulfate powder that solid content is >=99%；Again by nano-barium sulfate powder by spraying drying or microwave drying, or first using spraying drying, then microwave drying is carried out, obtain nano barium sulfate product.
Currently preferred, in step, described flocculation, sedimentation are specially：Sodium sulfate waste liquid and barium chloride solution are driven into settling tank respectively by pump, according to 1m310-20g flocculant polyvinyl lactams are added in sodium sulfate waste liquid or barium chloride solution, 12-36h is settled.
The SS values of the supernatant of above-mentioned two kinds of raw materials after flocculation, sedimentation are all 100-500 mg/L.
Currently preferred, in step, described coarse filtration is specially：By the supernatant of the two kinds of raw materials obtained by flocculation, sedimentation respectively through tow filter device coarse filtration, filtered using polypropylene fiber silk, filtering traffic is 20-30m3/h。
Currently preferred, in step, described essence filtering is specially：The supernatant of two kinds of raw materials Jing Guo coarse filtration is subjected to smart filtering respectively through membrane filtration, filtered using microfiltration membranes, the micro-filtration film thickness is 90-150 μm, the particle diameter of filtering is 0.025-10 μm, and operating pressure is 0.01-0.2MPa.
The mg/L of SS values≤100 of above-mentioned the pretreatment metabisulfite solution being filtrated to get by essence and pretreatment barium chloride solution, COD≤100, the barium chloride percentage by weight pre-processed in the sodium sulphate percentage by weight 90-95% in metabisulfite solution, pretreatment barium chloride solution is >=95%.
Currently preferred, in stepb, the micro passage reaction enters the bed of material, lower floor including upper strata and enters the bed of material and middle level conversion zone；The bed of material is entered on the upper strata and lower floor enters to be both provided with charging hole on the bed of material；The middle level conversion zone is netted branched structure, barium chloride feeding-passage is connected with sodium sulphate feeding-passage, constitutes feed unit, and two feed units are oppositely arranged, and connected simultaneously by one-level passage, the feed unit constitutes first order reaction unit with the one-level passage；Two first order reaction units are oppositely arranged, and are connected simultaneously by secondary passage, constitute second order reaction unit；Two second order reaction units are oppositely arranged, and are connected simultaneously by three-level passage, constitute third-order reaction unit；According to above-mentioned building form, each two N order reaction units are oppositely arranged, and are connected simultaneously by N+1 grades of passages, constitute N+1 order reaction units, the N+1 grades of passage is connected with tapping channel.
It is currently preferred, in stepb, in the course of reaction in described micro passage reaction：Reaction temperature is 25-40 DEG C, and flow is 50-500ml/min, and pressure is 0.3-0.5MPa, and the reaction time is 1-5s.
Currently preferred, described that the obtained nano barium sulfate slurries of step B are added into blood separation sedimentator in step C, the wash cycles that add water are specially：Nano barium sulfate slurry is added to blood separation sedimentator, separation of solid and liquid, after solid comes out, water content is 30%, add and blood separation sedimentator is again introduced into after water, until obtaining the nano-barium sulfate powder that solid content is >=99%, the rotating speed of blood separation sedimentator is 18000-20000r/min.
Currently preferred, in step C, the spraying drying is specially：The nano-barium sulfate powder addition water that sedimentator is obtained will be separated by blood, it is 50-70% to make water content, subsequently into spraying drying plant, and setting charging rate is 500-1000ml/min, and feeding temperature is 200-250 DEG C, and drop temperature is 100-130 DEG C.
Currently preferred, in step C, the microwave drying is specially：The nano-barium sulfate powder obtained by blood separation sedimentator or the nano-barium sulfate powder by spraying drying are directly entered microwave drying equipment, setting charging rate is 10-50kg/min, and drying temperature is 150-200 DEG C, and drying power is 150kw.
The advantageous effects that the present invention is brought：
1st, the present invention solves prior art and not carried out for sodium sulfate waste liquid in viscose rayon production, it is impossible to obtain the high nano-barium sulfate powder material of uniform particle, good dispersion, product quality.The characteristics of sodium sulfate waste liquid that the present invention is produced in being produced for viscose rayon, using specific pretreatment and the method for subsequent treatment, with reference to micro passage reaction, sodium sulfate waste liquid produces the high nano-barium sulfate powder material of uniform particle, good dispersion, product quality in being produced using viscose rayon, so that refuse reclamation, increase benefit, reduce the pollution of environment.
2nd, currently preferred, step A employs specific flocculation, sedimentation process.Can adsorbent particles, built bridge between particulate, promote to gather, and accelerate the coagulation of particle, reach the purpose of solid- liquid separation.After being settled after flocculation, impurity is significantly reduced, before not flocculating, and greatly, more than 3000mg/L, and solution is very muddy for SS values, with the presence of a large amount of suspensions, after being flocculated by appeal parameter, and SS values are that solution is more limpid without obvious suspension in 100-500mg/L, solution.It so also ensure that the nano barium sulfate of high-quality is made in the sodium sulfate waste liquid in being produced for viscose rayon.
3rd, it is currently preferred, specific tow filter device coarse filtration technique is employed in step A.The big impurity of filtering can either be played a part of, enable to follow-up membrane filtration to bear pressure again low, increase the service life.It so also ensure that the nano barium sulfate of high-quality is made in the sodium sulfate waste liquid in being produced for viscose rayon.
4th, it is currently preferred, the smart filtering technique of specific membrane filtration is employed in step A.After filtering, solution is as clear as crystal, almost free from admixture, will not block micro passage reaction.It so also ensure that the nano barium sulfate of high-quality is made in the sodium sulfate waste liquid in being produced for viscose rayon.
5th, it is currently preferred, the micro passage reaction of specific structure is employed in step B.The setting that the micro passage reaction passes through three-decker and reaction of high order unit, enable to charging more accurate, reaction mass mixing is more uniform, the laminar flow phenomenon for overcoming feed liquid to occur in head-on collision course of reaction, makes reaction be more nearly plume state, and course of reaction contact is more abundant, reaction is more thorough, the nano barium sulfate that head-on collision reaction generation can be prevented effectively from is reunited again, product is kept nano shape and uniform particle sizes, and then high-quality nano barium sulfate product is made.
6th, it is currently preferred, in stepb, in the course of reaction in described micro passage reaction：Reaction temperature is 25-40 DEG C, and flow is 50-500ml/min, and pressure is 0.3-0.5MPa, and the reaction time is 1-5s.The setting of above-mentioned parameter system, ensure that obtained high-quality nano barium sulfate product.
7th, it is currently preferred, in step C, using specific separation and stoving process method and technological parameter, it ensure that the nano barium sulfate of high-quality is made in the sodium sulfate waste liquid in being produced for viscose rayon.
Brief description of the drawings
Fig. 1 is conversion zone top view cross section structural representation in middle level of the present invention；
Fig. 2 is the mplifying structure schematic diagram of second order reaction unit of the present invention（A in Fig. 1）；
Fig. 3 is side structure schematic view of the present invention；
Fig. 4 is overlooked or present invention looks up structural representation for the present invention.
Reference：1 be upper strata enter the bed of material, 2 be lower floor enter the bed of material, 3 be middle level conversion zone, 4 be charging hole, 5 be barium chloride feeding-passage, 6 be sodium sulphate feeding-passage, 7 be one-level passage, 8 be secondary passage, 9 be three-level passage, 10 be tapping channel, 11 be six grades of passages, 12 be level Four passage, 13 be Pyatyi passage.
Embodiment
Embodiment 1
Sodium sulfate waste liquid produces the technique of nano barium sulfate in a kind of utilization viscose rayon production, comprises the following steps that：
A, pretreatment of raw material
Sodium sulfate waste liquid and barium chloride solution are respectively by flocculation, sedimentation during viscose rayon is produced, and the supernatant of two kinds of raw materials finally carries out smart filtering using membrane filtration again respectively through coarse filtration, obtains pretreatment metabisulfite solution and pre-process barium chloride solution；
B, metering and reaction
Step A is pre-processed into obtained metabisulfite solution and barium chloride solution by measuring pump-metered, micro passage reaction is squeezed into, prepares nano barium sulfate slurry；
C, subsequent treatment
The obtained nano barium sulfate slurries of step B are added to blood separation sedimentator, add water wash cycles, until obtaining the nano-barium sulfate powder that solid content is >=99%；Again by nano-barium sulfate powder by spraying drying or microwave drying, or first using spraying drying, then microwave drying is carried out, obtain nano barium sulfate product.
Embodiment 2
On the basis of embodiment 1：
It is preferred that, in step, described flocculation, sedimentation are specially：Sodium sulfate waste liquid and barium chloride solution are driven into settling tank respectively by pump, according to 1m310g flocculant polyvinyl lactams are added in sodium sulfate waste liquid or barium chloride solution, 12h is settled.
Further, the SS values of the supernatant of two kinds of raw materials after flocculation, sedimentation are all 100 mg/L.
It is preferred that, in step, described coarse filtration is specially：By the supernatant of the two kinds of raw materials obtained by flocculation, sedimentation respectively through tow filter device coarse filtration, filtered using polypropylene fiber silk, filtering traffic is 20m3/h。
It is preferred that, in step, described essence filtering is specially：The supernatant of two kinds of raw materials Jing Guo coarse filtration is subjected to smart filtering respectively through membrane filtration, filtered using microfiltration membranes, the micro-filtration film thickness is 90 μm, the particle diameter of filtering is 0.025 μm, and operating pressure is 0.01MPa.
Further, the mg/L of SS values≤100 of the pretreatment metabisulfite solution being filtrated to get by essence and pretreatment barium chloride solution, barium chloride percentage by weight in sodium sulphate percentage by weight 90% in COD≤100, pretreatment metabisulfite solution, pretreatment barium chloride solution is >=95%.
Embodiment 3
On the basis of embodiment 1：
It is preferred that, in step, described flocculation, sedimentation are specially：Sodium sulfate waste liquid and barium chloride solution are driven into settling tank respectively by pump, according to 1m320g flocculant polyvinyl lactams are added in sodium sulfate waste liquid or barium chloride solution, 36h is settled.
Further, the SS values of the supernatant of two kinds of raw materials after flocculation, sedimentation are all 500 mg/L.
It is preferred that, in step, described coarse filtration is specially：By the supernatant of the two kinds of raw materials obtained by flocculation, sedimentation respectively through tow filter device coarse filtration, filtered using polypropylene fiber silk, filtering traffic is 30m3/h。
It is preferred that, in step, described essence filtering is specially：The supernatant of two kinds of raw materials Jing Guo coarse filtration is subjected to smart filtering respectively through membrane filtration, filtered using microfiltration membranes, the micro-filtration film thickness is 150 μm, the particle diameter of filtering is 10 μm, and operating pressure is 0.2MPa.
Further, the mg/L of SS values≤100 of the pretreatment metabisulfite solution being filtrated to get by essence and pretreatment barium chloride solution, barium chloride percentage by weight in sodium sulphate percentage by weight 95% in COD≤100, pretreatment metabisulfite solution, pretreatment barium chloride solution is >=95%.
Embodiment 4
On the basis of embodiment 1：
It is preferred that, in step, described flocculation, sedimentation are specially：Sodium sulfate waste liquid and barium chloride solution are driven into settling tank respectively by pump, according to 1m315g flocculant polyvinyl lactams are added in sodium sulfate waste liquid or barium chloride solution, 24h is settled.
Further, the SS values of the supernatant of two kinds of raw materials after flocculation, sedimentation are all 300 mg/L.
It is preferred that, in step, described coarse filtration is specially：By the supernatant of the two kinds of raw materials obtained by flocculation, sedimentation respectively through tow filter device coarse filtration, filtered using polypropylene fiber silk, filtering traffic is 25m3/h。
It is preferred that, in step, described essence filtering is specially：The supernatant of two kinds of raw materials Jing Guo coarse filtration is subjected to smart filtering respectively through membrane filtration, filtered using microfiltration membranes, the micro-filtration film thickness is 120 μm, the particle diameter of filtering is 5 μm, and operating pressure is 0.1MPa.
Further, the mg/L of SS values≤100 of the pretreatment metabisulfite solution being filtrated to get by essence and pretreatment barium chloride solution, barium chloride percentage by weight in sodium sulphate percentage by weight 92.5% in COD≤100, pretreatment metabisulfite solution, pretreatment barium chloride solution is >=95%.
Embodiment 5
On the basis of embodiment 1：
It is preferred that, in step, described flocculation, sedimentation are specially：Sodium sulfate waste liquid and barium chloride solution are driven into settling tank respectively by pump, according to 1m312g flocculant polyvinyl lactams are added in sodium sulfate waste liquid or barium chloride solution, 30h is settled.
Further, the SS values of the supernatant of two kinds of raw materials after flocculation, sedimentation are all 200 mg/L.
It is preferred that, in step, described coarse filtration is specially：By the supernatant of the two kinds of raw materials obtained by flocculation, sedimentation respectively through tow filter device coarse filtration, filtered using polypropylene fiber silk, filtering traffic is 21m3/h。
It is preferred that, in step, described essence filtering is specially：The supernatant of two kinds of raw materials Jing Guo coarse filtration is subjected to smart filtering respectively through membrane filtration, filtered using microfiltration membranes, the micro-filtration film thickness is 145 μm, the particle diameter of filtering is 0.1 μm, and operating pressure is 0.05MPa.
Further, the mg/L of SS values≤100 of the pretreatment metabisulfite solution being filtrated to get by essence and pretreatment barium chloride solution, barium chloride percentage by weight in sodium sulphate percentage by weight 94% in COD≤100, pretreatment metabisulfite solution, pretreatment barium chloride solution is >=95%.
Embodiment 6
On the basis of embodiment 1：
It is preferred that, in stepb, the micro passage reaction enters the bed of material 1, lower floor including upper strata and enters the bed of material 2 and middle level conversion zone 3；The bed of material 1 is entered on the upper strata and lower floor enters to be both provided with charging hole 4 on the bed of material 2；The middle level conversion zone 3 is netted branched structure, barium chloride feeding-passage 5 is connected with sodium sulphate feeding-passage 6, constitutes feed unit, and two feed units are oppositely arranged, and connected simultaneously by one-level passage 7, the feed unit constitutes first order reaction unit with the one-level passage 7；Two first order reaction units are oppositely arranged, and are connected simultaneously by secondary passage 8, constitute second order reaction unit；Two second order reaction units are oppositely arranged, and are connected simultaneously by three-level passage 9, constitute third-order reaction unit；According to above-mentioned building form, each two N order reaction units are oppositely arranged, and are connected simultaneously by N+1 grades of passages, constitute N+1 order reaction units, the N+1 grades of passage is connected with tapping channel 10.
Micro passage reaction internal structure of the present invention is fine, reticulate, raw material is after charging hole 4, the netted passage fast reaction of layer conversion zone 3 in the reactor, the reaction time was controlled within 1 second, and the nano barium sulfate of generation is continuously expelled in slurry collection groove through tapping channel 10.
Embodiment 7
On the basis of embodiment 6：
It is preferred that, the tapping channel 10 is connected with six grades of passages 11.Six order reaction units are set, the balance of product quality, production efficiency and production cost is enabled to, additionally it is possible to ensure that discharging is more uniform, unobstructed.Now N is that five, N+1 is six, and six order reaction units are one, and is end reaction unit.Now the composition of the micro passage reaction is：Middle level conversion zone 3 is netted branched structure, barium chloride feeding-passage 5 is connected with sodium sulphate feeding-passage 6, constitutes feed unit, and two feed units are oppositely arranged, and connected simultaneously by one-level passage 7, the feed unit constitutes first order reaction unit with the one-level passage 7；Two first order reaction units are oppositely arranged, and are connected simultaneously by secondary passage 8, constitute second order reaction unit；Two second order reaction units are oppositely arranged, and are connected simultaneously by three-level passage 9, constitute third-order reaction unit；Two third-order reaction units are oppositely arranged, and are connected simultaneously by level Four passage 12, constitute fourth-order reaction unit；Two fourth-order reaction units are oppositely arranged, and are connected simultaneously by Pyatyi passage 13, constitute Pyatyi reaction member；Two Pyatyi reaction members are oppositely arranged, and are connected simultaneously by six grades of passages 11, constitute six order reaction units；Six grades of passages 11 are connected with the tapping channel 10.
It is preferred that, the caliber of all passages is less than or equal to 10um.The setting of the caliber can be prevented effectively from reaction product reunion.
It is preferred that, the charging hole 4 is multiple evenly distributed micropores.The setting of the charging hole reacts uniformity after ensure that charging, and feed pressure is consistent, it is ensured that frontal impact dynamics.
It is preferred that, the aperture of the charging hole 4 is less than or equal to 10um.The setting in the charging aperture aperture ensure that the uniformity of charging.
It is preferred that, the micro passage reaction is made up of Hastelloy.Enable to micro passage reaction more corrosion-resistant, durable using the material.
It is preferred that, the barium chloride feeding-passage 5 is relative with the sodium sulphate feeding-passage 6 and be arranged in parallel.It is arranged in parallel on the basis of being oppositely arranged, the dynamics of head-on crash and head-on crash is ensure that, reaction is more effective.
It is preferred that, with relative between first order reaction unit and be arranged in parallel.It is arranged in parallel on the basis of being oppositely arranged, it can arrange even closer, reasonable, also ensure that the dynamics of head-on crash and head-on crash, reaction is more effective.
It is preferred that, in the first order reaction unit, barium chloride feeding-passage 5 and sodium sulphate feeding-passage 6 in two feed units being oppositely arranged stagger setting.So set and ensure that upper level unreacted thoroughly raw material is complete in next order reaction.
It is preferred that, the charging hole 4 that the bed of material 1 is entered on the upper strata is connected with the barium chloride feeding-passage 5, and the lower floor enters the charging hole of the bed of material 2 and connected with sodium sulphate feeding-passage 6 described in 4.The setting ensure that charging is uniform.
Embodiment 8
In embodiment 1 or on the basis of embodiment 6：
It is preferred that, in stepb, in the course of reaction in described micro passage reaction：Reaction temperature is 25 DEG C, and flow is 50ml/min, and pressure is 0.3MPa, and the reaction time is 1s.
Embodiment 9
In embodiment 1 or on the basis of embodiment 6：
It is preferred that, in stepb, in the course of reaction in described micro passage reaction：Reaction temperature is 40 DEG C, and flow is 500ml/min, and pressure is 0.5MPa, and the reaction time is 5s.
Embodiment 10
In embodiment 1 or on the basis of embodiment 6：
It is preferred that, in stepb, in the course of reaction in described micro passage reaction：Reaction temperature is 33 DEG C, and flow is 275ml/min, and pressure is 0.4MPa, and the reaction time is 3s.
Embodiment 11
In embodiment 1 or on the basis of embodiment 6：
It is preferred that, in stepb, in the course of reaction in described micro passage reaction：Reaction temperature is 39 DEG C, and flow is 300ml/min, and pressure is 0.35MPa, and the reaction time is 1.5s.
Embodiment 12
On the basis of embodiment 1：
It is preferred that, described that the obtained nano barium sulfate slurries of step B are added into blood separation sedimentator in step C, the wash cycles that add water are specially：Nano barium sulfate slurry is added to blood separation sedimentator, separation of solid and liquid, after solid comes out, water content is 30%, add and blood separation sedimentator is again introduced into after water, until obtaining the nano-barium sulfate powder that solid content is >=99%, the rotating speed of blood separation sedimentator is 18000r/min.
It is preferred that, in step C, the spraying drying is specially：The nano-barium sulfate powder addition water that sedimentator is obtained will be separated by blood, it is 50% to make water content, subsequently into spraying drying plant, and setting charging rate is 500ml/min, and feeding temperature is 200 DEG C, and drop temperature is 100 DEG C.
It is preferred that or it is further, in step C, the microwave drying is specially：The nano-barium sulfate powder obtained by blood separation sedimentator or the nano-barium sulfate powder by spraying drying are directly entered microwave drying equipment, setting charging rate is 10kg/min, and drying temperature is 150 DEG C, and drying power is 150kw.
Embodiment 13
On the basis of embodiment 1：
It is preferred that, described that the obtained nano barium sulfate slurries of step B are added into blood separation sedimentator in step C, the wash cycles that add water are specially：Nano barium sulfate slurry is added to blood separation sedimentator, separation of solid and liquid, after solid comes out, water content is 30%, add and blood separation sedimentator is again introduced into after water, until obtaining the nano-barium sulfate powder that solid content is >=99%, the rotating speed of blood separation sedimentator is 20000r/min.
It is preferred that, in step C, the spraying drying is specially：The nano-barium sulfate powder addition water that sedimentator is obtained will be separated by blood, it is 70% to make water content, subsequently into spraying drying plant, and setting charging rate is 1000ml/min, and feeding temperature is 250 DEG C, and drop temperature is 130 DEG C.
It is preferred that or it is further, in step C, the microwave drying is specially：The nano-barium sulfate powder obtained by blood separation sedimentator or the nano-barium sulfate powder by spraying drying are directly entered microwave drying equipment, setting charging rate is 50kg/min, and drying temperature is 200 DEG C, and drying power is 150kw.
Embodiment 14
On the basis of embodiment 1：
It is preferred that, described that the obtained nano barium sulfate slurries of step B are added into blood separation sedimentator in step C, the wash cycles that add water are specially：Nano barium sulfate slurry is added to blood separation sedimentator, separation of solid and liquid, after solid comes out, water content is 30%, add and blood separation sedimentator is again introduced into after water, until obtaining the nano-barium sulfate powder that solid content is >=99%, the rotating speed of blood separation sedimentator is 19000r/min.
It is preferred that, in step C, the spraying drying is specially：The nano-barium sulfate powder addition water that sedimentator is obtained will be separated by blood, it is 60% to make water content, subsequently into spraying drying plant, and setting charging rate is 750ml/min, and feeding temperature is 225 DEG C, and drop temperature is 115 DEG C.
It is preferred that or it is further, in step C, the microwave drying is specially：The nano-barium sulfate powder obtained by blood separation sedimentator or the nano-barium sulfate powder by spraying drying are directly entered microwave drying equipment, setting charging rate is 30kg/min, and drying temperature is 175 DEG C, and drying power is 150kw.
Embodiment 15
On the basis of embodiment 1：
Described that the obtained nano barium sulfate slurries of step B are added into blood separation sedimentator in step C, the wash cycles that add water are specially：Nano barium sulfate slurry is added to blood separation sedimentator, separation of solid and liquid, after solid comes out, water content is 30%, add and blood separation sedimentator is again introduced into after water, until obtaining the nano-barium sulfate powder that solid content is >=99%, the rotating speed of blood separation sedimentator is 19500r/min.
It is preferred that, in step C, the spraying drying is specially：The nano-barium sulfate powder addition water that sedimentator is obtained will be separated by blood, it is 55% to make water content, subsequently into spraying drying plant, and setting charging rate is 900ml/min, and feeding temperature is 210 DEG C, and drop temperature is 120 DEG C.
It is preferred that or it is further, in step C, the microwave drying is specially：The nano-barium sulfate powder obtained by blood separation sedimentator or the nano-barium sulfate powder by spraying drying are directly entered microwave drying equipment, setting charging rate is 15kg/min, and drying temperature is 190 DEG C, and drying power is 150kw.
Embodiment 16
Comparative experimental data, control group one is only is pre-processed, and control group two is only has carried out subsequent treatment, and experimental group is pre-processed and subsequent treatment to employ the present invention.
Embodiment 17
400 kilograms of technical grade barium chlorides are dissolved in the solution that water is configured to 0.9mol/L in barium chloride dissolving tank, is squeezed into by the security filter for controlling barium chloride in barium chloride holding vessel and injects reactor by barium chloride to stockline.In glauber salt dissolving tank, by the ratio between amount of barium chloride and sodium sulphate pure material 1:The 1 corresponding waste residue glauber salt of dissolving, squeezes into glauber salt holding vessel by the security filter for controlling glauber salt and injects conventional micro passage reaction to stockline by glauber salt.Nano barium sulfate in collecting tank is subjected to separation of solid and liquid by sedimentation-type centrifuge, solid is packaged to be 448 kilograms of nano barium sulfate products after drying, and liquid obtains Nacl sodium chloride by evaporative crystallization.
Embodiment 18
400 kilograms of technical grade barium chlorides are dissolved in the solution that water is configured to 0.9mol/L in barium chloride dissolving tank, is squeezed into by the security filter for controlling barium chloride in barium chloride holding vessel and injects reactor by barium chloride to stockline.In glauber salt dissolving tank, by the ratio between amount of barium chloride and sodium sulphate pure material 1:The 1 corresponding waste residue glauber salt of dissolving, squeezes into glauber salt holding vessel by the security filter for controlling glauber salt and injects the micro passage reaction of currently preferred specific structure to stockline by glauber salt.Nano barium sulfate in collecting tank is subjected to separation of solid and liquid by sedimentation-type centrifuge, solid is packaged to be 448 kilograms of nano barium sulfate products after drying, and liquid obtains Nacl sodium chloride by evaporative crystallization.
Embodiment 19
400 kilograms of technical grade barium chlorides are dissolved in the solution that water is configured to 1.2mol/L in barium chloride dissolving tank, is squeezed into by the security filter for controlling barium chloride in barium chloride holding vessel and injects reactor by barium chloride to stockline.In glauber salt dissolving tank, by the ratio between amount of barium chloride and sodium sulphate pure material 1:The 1 corresponding waste residue glauber salt of dissolving, squeezes into glauber salt holding vessel by the security filter for controlling glauber salt and injects non-micro passage reaction to stockline by glauber salt（In General reactions device）.Nano barium sulfate in collecting tank is subjected to separation of solid and liquid by sedimentation-type centrifuge, solid is packaged to be 448 kilograms of nano barium sulfate products after drying, and liquid obtains Nacl sodium chloride by evaporative crystallization.
Embodiment 20
Claims (11)
1. the technique that sodium sulfate waste liquid produces nano barium sulfate in a kind of utilization viscose rayon production, it is characterised in that：Comprise the following steps that：
A, pretreatment of raw material
Sodium sulfate waste liquid and barium chloride solution are respectively by flocculation, sedimentation during viscose rayon is produced, and the supernatant of two kinds of raw materials finally carries out smart filtering using membrane filtration again respectively through coarse filtration, obtains pretreatment metabisulfite solution and pre-process barium chloride solution；
B, metering and reaction
Step A is pre-processed into obtained metabisulfite solution and barium chloride solution by measuring pump-metered, micro passage reaction is squeezed into, prepares nano barium sulfate slurry；
C, subsequent treatment
The obtained nano barium sulfate slurries of step B are added to blood separation sedimentator, add water wash cycles, until obtaining the nano-barium sulfate powder that solid content is >=99%；Again by nano-barium sulfate powder by spraying drying or microwave drying, or first using spraying drying, then microwave drying is carried out, obtain nano barium sulfate product.
2. the technique that sodium sulfate waste liquid produces nano barium sulfate in a kind of utilization viscose rayon production according to claim 1, it is characterised in that：In step, described flocculation, sedimentation be specially：Sodium sulfate waste liquid and barium chloride solution are driven into settling tank respectively by pump, according to 1m310-20g flocculant polyvinyl lactams are added in sodium sulfate waste liquid or barium chloride solution, 12-36h is settled.
3. the technique that sodium sulfate waste liquid produces nano barium sulfate in a kind of utilization viscose rayon production according to claim 2, it is characterised in that：The SS values of the supernatant of two kinds of raw materials after flocculation, sedimentation are all 100-500 mg/L.
4. the technique that sodium sulfate waste liquid produces nano barium sulfate in a kind of utilization viscose rayon production according to claim 1, it is characterised in that：In step, described coarse filtration is specially：By the supernatant of the two kinds of raw materials obtained by flocculation, sedimentation respectively through tow filter device coarse filtration, filtered using polypropylene fiber silk, filtering traffic is 20-30m3/h。
5. the technique that sodium sulfate waste liquid produces nano barium sulfate in a kind of utilization viscose rayon production according to claim 1, it is characterised in that：In step, described essence, which is filtered, is specially：The supernatant of two kinds of raw materials Jing Guo coarse filtration is subjected to smart filtering respectively through membrane filtration, filtered using microfiltration membranes, the micro-filtration film thickness is 90-150 μm, the particle diameter of filtering is 0.025-10 μm, and operating pressure is 0.01-0.2MPa.
6. the technique that sodium sulfate waste liquid produces nano barium sulfate in a kind of utilization viscose rayon production according to claim 5, it is characterised in that：The mg/L of SS values≤100 of the pretreatment metabisulfite solution being filtrated to get by essence and pretreatment barium chloride solution, COD≤100, the barium chloride percentage by weight pre-processed in the sodium sulphate percentage by weight 90-95% in metabisulfite solution, pretreatment barium chloride solution is >=95%.
7. the technique that sodium sulfate waste liquid produces nano barium sulfate in a kind of utilization viscose rayon production according to claim 1, it is characterised in that：In stepb, the micro passage reaction enters the bed of material including upper strata（1）, lower floor enter the bed of material（2）And middle level conversion zone（3）；The bed of material is entered on the upper strata（1）Enter the bed of material with lower floor（2）On be both provided with charging hole（4）；The middle level conversion zone（3）For netted branched structure, barium chloride feeding-passage（5）With sodium sulphate feeding-passage（6）Connection, constitutes feed unit, two feed units are oppositely arranged, and pass through one-level passage simultaneously（7）Connection, the feed unit and the one-level passage（7）Constitute first order reaction unit；Two first order reaction units are oppositely arranged, and pass through secondary passage simultaneously（8）Connection, constitutes second order reaction unit；Two second order reaction units are oppositely arranged, and pass through three-level passage simultaneously（9）Connection, constitutes third-order reaction unit；According to above-mentioned building form, each two N order reaction units are oppositely arranged, and are connected simultaneously by N+1 grades of passages, constitute N+1 order reaction units, the N+1 grades of passage and tapping channel（10）Connection.
8. the technique that sodium sulfate waste liquid produces nano barium sulfate in a kind of utilization viscose rayon production according to claim 1 or 7, it is characterised in that：In stepb, in the course of reaction in described micro passage reaction：Reaction temperature is 25-40 DEG C, and flow is 50-500ml/min, and pressure is 0.3-0.5MPa, and the reaction time is 1-5s.
9. the technique that sodium sulfate waste liquid produces nano barium sulfate in a kind of utilization viscose rayon production according to claim 1, it is characterised in that：Described that the obtained nano barium sulfate slurries of step B are added into blood separation sedimentator in step C, the wash cycles that add water are specially：Nano barium sulfate slurry is added to blood separation sedimentator, separation of solid and liquid, after solid comes out, water content is 30%, add and blood separation sedimentator is again introduced into after water, until obtaining the nano-barium sulfate powder that solid content is >=99%, the rotating speed of blood separation sedimentator is 18000-20000r/min.
10. the technique that sodium sulfate waste liquid produces nano barium sulfate in a kind of utilization viscose rayon production according to claim 1, it is characterised in that：In step C, the spraying drying is specially：The nano-barium sulfate powder addition water that sedimentator is obtained will be separated by blood, it is 50-70% to make water content, subsequently into spraying drying plant, and setting charging rate is 500-1000ml/min, and feeding temperature is 200-250 DEG C, and drop temperature is 100-130 DEG C.
11. the technique that sodium sulfate waste liquid produces nano barium sulfate in a kind of utilization viscose rayon production according to claim 1 or 9, it is characterised in that：In step C, the microwave drying is specially：The nano-barium sulfate powder obtained by blood separation sedimentator or the nano-barium sulfate powder by spraying drying are directly entered microwave drying equipment, setting charging rate is 10-50kg/min, and drying temperature is 150-200 DEG C, and drying power is 150kw.
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| CN111977679A (en) * | 2020-07-21 | 2020-11-24 | 江苏阿尔法药业有限公司 | Treatment method of wastewater containing sodium sulfate and sodium chloride |
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