CN1076721A - Be suitable as the particulate manufacture method of stain remover, washing composition and/or clean-out system - Google Patents
Be suitable as the particulate manufacture method of stain remover, washing composition and/or clean-out system Download PDFInfo
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- CN1076721A CN1076721A CN 93101453 CN93101453A CN1076721A CN 1076721 A CN1076721 A CN 1076721A CN 93101453 CN93101453 CN 93101453 CN 93101453 A CN93101453 A CN 93101453A CN 1076721 A CN1076721 A CN 1076721A
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Abstract
In the normal pressure scope and in the fluidizing agent of heat, make particle by the aqueous solution and/or suspension by fluidized bed spray granulation.Adopt superheated vapour to operate, before particle suffers damage because of the effect of heat, it is discharged in by nodulizer as fluidizing agent.In case of necessity, can guarantee above-mentioned graininess and free-running property of passing through the shelf-stable of part exsiccant material in conjunction with the mix ingredients of the confined water yield and/or by aftertreatment by adding.Water steam cycle air-flow is operated in the system of sealing, and as shunting, and liberated heat infeeds in this system again by the transpiring moisture of extracting the material of packing in this system out.Implement this method and can not produce waste gas and waste water, when extensive the use, can not cause gained particulate quality deterioration.
Description
The present invention relates to a kind ofly make the granulous of this active substance and/or active substance mixture and the method for loose granule by the aqueous solution and/or the suspension of a kind of active substance or active substance mixture by fluidized bed spray granulation in the fluidizing agent of heat He in the normal pressure scope, described active substance and/or active substance mixture are suitable as stain remover, washing composition and/or clean-out system and/or are suitable in these chemicals.
In order to make particle, on industrial application, especially can consider to adopt the spraying dehydration, have spraying dehydration and fluidized bed spray granulation that fluidized-bed becomes granule by initial product liquid (ie in solution or suspension).Over past ten years, in the world, greatly in commercial quantity making particle by the moisture formulation of the active substance of mentioned kind generally all is to adopt the spraying dehydration method.The mixture of the combustion exhaust of use warm air or air and heat is as drying air stream.Fabric washing powder and be used to make in pelletized form active substance and active substance mixture with the fabric detergent of bulky powder shape, be in so-called spraying or washing tower, usually under the environmental stress scope with the big industrial-scale production of reflux type (under rare occasion with concurrent).
The method that adopts fluidized bed spray granulation to make detergent particles is (Uhlemann in Chem.-Ing.-Tech.62(1990) well known in the prior art Nr.10, S.822-834 and EP-B-163836).Though in the method for stain remover, washing composition and the clean-out system of this shape that seldom is used for making powder, the solid particle remains in the air-flow upwards with suspension.Each particle separates each other in this state, and therefore, when liquid was sprayed into fluidized-bed, the drop that sprays into can touch around the particulate.In addition, intensive heat exchange and mass transfer have taken place between solid particulate and the air-flow in this state.
When the drop that is sprayed into when particles suspended permeated, the product liquid that sprays into drop just was distributed to below the top layer fully by expansion.Cause liquid film drying and fixed with this intensive heat exchange and the mass transfer of air-flow on every side.Blend fixedly through repeatedly spraying, expanding, particle has been grown up as onion.Particle with desirable granularity is fine and close, approaches garden shape.
When the moisture preparation with above-mentioned substance carries out fluidized bed spray granulation, with warm air as fluidizing agent the same operation of when dehydration of spraying.In addition, also mentioned use nitrogen among the EP-B-163836.
Except the random operability of gas phase, can in an open system, operate, to have that the hot gas of moisture is technical to be discharged into without a doubt in the ambient atmosphere and can not to produce any worry, this also is regarded as doing with warm air a big advantage of the drying means of dry gas.The result who drying process is carried out deep physical-chemical research shows that when using hot-air dry, even adopt the relatively mild hot gas temperature that compares, drying is still very effective and carry out very soon.Under the lower situation of particle temperature, for example the particulate temperature is when 40 ℃ of left and right sides, the drying process of wet particle has begun, at this moment, its drying process is irrelevant with the temperature of employed hot gas to a great extent, along with the proceeding of drying process, particle temperature rises to the boiling temperature of water more lentamente under normal pressure.Generally speaking, drying process is carried out comparatively fast in warm air, and just in last drying stage drying process also very effective, therefore, above-mentioned active substance has born comparatively gentle temperature load when drying forms bulk material.
For the active substance of fabric detergent involved in the present invention and/or clean-out system or this professional skill field of drying and dehydrating of active substance mixture, the typical shortcoming of aforesaid method and restriction can be enumerated as follows: having a variety of in these active substances is easy oxidations, particularly all the more so under the situation of organic constituent.Use hot air treatment, particularly under comparatively high temps, handle, may cause this active principle to suffer damage.Organically or to a great extent be organic active substance purely, for example based on the active substance of the tensio-active agent of natural compounds, when drying owing to dried material exist burning or even the danger of blast cause very big difficulty.Important active substance component, the nonionogenic tenside of detergent applications (Niotenside) particularly, more or less show intensive (Pluming) tendency in varying degrees, be about to the waste gas that has steam that organic aerosol is transformed into the spray washing tower.In a word, because a large amount of aqueous, solid-state and gasiform material and subsidiary material through processing exist the danger of serious environment pollution.At present, in the sector application of this method, the viewpoint that recycles drying air stream is embodied as yet fully.
In addition, when carrying out fluidised bed drying, people also know and can use hot steam to replace warm air as dry gas (Gehrmann, Chem.-Ing.-Tech.62(1990) Nr.10, S.A512-A520), at this moment, the refuse of discharge (waste water, waste gas) is few especially, and wherein the water vapor of Pai Chuing is condensed.Yet according to the prior art, this method can only be used for the product responsive relatively to temperature, for example brown coal or mud.In addition, also mentioned pulp dryer as its Application Areas.Also suggestion in a document uses vacuum drier to overflow to reduce refuse when thermally sensitive product carries out drying, but the document points out again simultaneously, is difficult to make the device that loose pine dress material is housed to turn round continuously.
Also occurred some problems when thermally sensitive product carries out drying in the steam fluidized bed dryer, promptly in 150 ℃ of left and right sides temperature ranges, the rate of drying when adopting superheated vapour is starkly lower than the rate of drying when using warm air.When having only working temperature to rise to 250 ℃, the rate of drying of the two just reaches unanimity.Therefore, when using superheated vapour as dry gas, have only the higher working temperature of employing in the time active substance drying of mentioned kind to be reached common desired residual moisture content at acceptable, and under high like this working temperature, the material of packing into will produce the temperature infringement that no longer can allow.
Therefore, task of the present invention is, improves aforesaid method, makes not produce waste gas and waste water when this method of enforcement, and simultaneously, when using this method on a large scale, it is inferior that prepared granular mass can not become industrial.
According to the present invention, this task realizes by following measure: adopt superheated vapour to carry out work as fluidizing agent, before particle is endangered because of the effect of heat, it is discharged from nodulizer, and thisly can and/or guarantee the graininess and the loose performance of its anti-storage by aftertreatment in conjunction with the blending ingredients of confined moisture by adding through part exsiccant material; In addition, in the system of sealing, use the work of water vapor cycling stream, from this system, extract the steaming waste water branch of the material of packing into out as shunting, and the restock heat energy of emitting.The supply of energy can be outside drying receptacle realizes and/or the person realizes by the interchanger that is provided with in drying receptacle by water vapor is overheated.
In old German patent application DE-A4030688, a kind of in small, broken bits, solid, accumulation and the loose active substance or method of active substance mixture that is used for stain remover, washing composition and/or clean-out system by its aqueous preparation manufacturing described, wherein, use superheated vapour as the exsiccant hot gas flow, and before partial material suffers damage owing to hot effect, just end its drying process.If necessary, this process part exsiccant material can be by adding graininess or the free-running property that certain can assign to guarantee its anti-storage in conjunction with the combined group of confined moisture.In addition or replace this measure, can also replenish and carry out an aftertreatment, so that the residual moisture content homogenizing in the partial material and/or under the condition of not damaging active substance, carry out once follow-up drying again.
, in this old patent application, be to adopt the spraying dehydration method to produce particle.Regulation is only randomly dry in fluidized-bed when carrying out aftertreatment through the exsiccant material.
Hereinafter described invention relates to carries out autotelic improvement and development to the method for above-mentioned old patent application.Because disclosure of the Invention is complete, the disclosure in above-mentioned old patent application obviously also becomes theme of the present invention like this.
In this regard, it should be noted that using superheated vapour up to now is very limited as the practical experience that dry gas carries out drying process, although this technology itself is just known and repeatedly described in the literature from the beginning of this century.Old patent application DE-A4030688 separates in detail with the prior art of related publication.This respect sees also the description of above-mentioned old patent application and only points out following publication, and these publications comprise the far-ranging document list that relates to this technical field):
A.M.Trommelen et al.“Eyaporation and Drying of Drops in Superheated Vapors”AIChE Journal 16（1970）857-867;Colin Beeby et al.“STEAM DRYING”Plenary Lecture，Proc.4th Int.Drying Sym.Kyoto（eds.R.Toei and Arun S.Mujumdar）1984，Bd.1，51-68 sowie W.A.Stein“Berechnung der Verdampfung von Flüssigkeit aus feuchten Produk-ten im Sprühturm”Verfahrenstechnik 7（1973）262-267.
With hot-air dry and between with the superheated vapour drying, a principle distinction important for understanding the present invention is obviously arranged, promptly when working with warm air, drying process has just very effectively begun under lower temperature of charge.And the minimizing of water content seems so obviously, so that when temperature of charge reached 100 ℃ of left and right sides, drying process was near finishing.For example have in the whole moisture that exist this moment like this and from drop, discharge up to about 90%.The temperature course of drop then seems different fully when using hot steam.Because heat steam condensation and heat of condensation passed to need the exsiccant material on the colder material of packing into, water droplet spontaneously is heated to the boiling temperature of water under working conditions, is heated to about 100 ℃ temperature when that is to say under normal pressure operation.Between whole dry epoch, during dripping, the thing lining remains this boiling temperature as minimum temperature.Adding the water that contains the dry substance that will obtain each time all causes sooner or later-depends on the degree of drying-temperature course of drop upwards to depart from.
In the method for the invention, exactly when temperature sensitive dried material involved in the present invention, be tolerated in certain restriction of the dry aspect as a result of final product wittingly, in the fluidized bed spray granulation method, utilize the various advantages of bringing by superheated vapour replacement warm air.As a basic feature, the present invention's regulation, in dried material, can allow residual water-content, the various specific situations of these residual moistures-depend on-can be sizable, but guarantee to carry out aftertreatment, for example follow-up drying simultaneously or by the auxiliary agent that uses together through the graininess of the anti-storage of above-mentioned dried particulate material and free-running property and/or regulation.Described auxiliary agent is as also will being illustrated hereinafter, and they can be the active substances of selecting to be used for predetermined application target, perhaps can be inert substances.Therefore, according to the present invention, successfully reached the well-known complicated quality standard that requires to the multiple substance mixture based on organic and inorganic mixing element involved in the present invention (for example fabric detergent), and do not damage quality, but be under the situation of performance, to realize with superheated vapour exsiccant advantage.The oxidation style that the composition of stain remover, washing composition and clean-out system is produced harm bans use of; The danger of burning and blast is excluded.Because dry steam is circular flow, therefore unwelcome composition is not discharged in the ambient atmosphere, is only drawn and required by the steam diversion that will carry out producing in the exsiccant material to purify.This moment, the subsidiary material that carries together that produces partly obtained utilizing.Common technological merit also can be beneficial to the layout of related device.
The energy input that carries out in the export-oriented steam cycle of fluidized-bed can adopt any known mode to carry out, but, preferably adopt indirect heat transfer, for example use tube bundle system, one effluent of this tube bundle system is crossed the hot gas in any source, and opposite side-separate-then flow through the water vapor that will heat flows with this hot gas.
In the embodiment of a particularly important of the present invention, it is this that energy is infeeded cyclic steam stream indirectly is to realize to the vapour stream indirect heat transfer by means of the burner of one or more formation one, wherein, in burner one side, the combustion gases of heat are directly imported in the heat exchanger that is arranged in the steam cycle air-flow.The temperature of combustion gases for example can be in about 400-1000 ℃ scope, preferably in about 650-860 ℃ temperature range.For obtain optimal heat efficient and thereby reduce the cost of total technological process, conform with purpose and be, also regulation recycles a part, waste gas as much as possible preferably.Like this, for example can be with 30%(volume at least), 40%(volume preferably) more than leave the heat of bonded heat exchanger waste gas send back in the working cycle, further utilize its heat energy.The quantity of the waste gas that especially recycles preferably accounts for the 60%(volume of the combustion gases that infeed) more than, commonly used is at the 70%(volume) about scope in.All habitual combustion gas all are fit to make said burner work, especially Sweet natural gas or similar lower hydrocarbon or hydrocarbon mixture and/or person's hydrogen.
In the method for the invention, mainly be to come to the hot steam heat supply by the interchanger that is positioned at inside or outside, wherein hot steam is as transmission medium.By reliably, fully having got rid of the aggressiveness material in the dry gas, oxygen and carbon dioxide particularly, avoided equally wanting dried material not wish the oxidation corrosion that takes place, for example generate carbonate or carbonate sediment, this situation is inevitable in the most of alkaline active substance in technical field involved in the present invention when operating with the dry gas that contains waste gas.Can realize especially effectively heat exchange with the heat exchanger supplementary heating that is located in the fluidized-bed, and than heating by importing hot steam uniquely, in order to obtain identical residual water-content, the temperature of steam can allow much lower, thereby has reduced the thermal load that needs dried material.This improved method is particularly suitable for the dried material to the medium sensitivity of temperature.When heat sensitive active substance and active substance mixture are carried out drying, advantageously use the outside heat exchanger that connects, it is shorter than the situation that heat exchanger is set in the fluidized-bed to control the residence time in this case.
According to the present invention, in a closed system with water vapor circulating current, to operate, the material moisture evaporated of will packing into from this system is extracted out, and the energy that will especially emit in drying step sends back in the circulating current simultaneously.In an important embodiment, the water vapor shunting that is given off is used separately as useful steam after having removed the material component of packing into that wherein carries, because if requirement is arranged, at first the pressure and temperature of these steam diversion is fit to the desired condition in there.In another embodiment of the inventive method, the steam shunting condensation that a part is discharged is to conform with purpose.The produced simultaneously aqueous liquid phase of this moment institute preferably is being used for preparing the aqueous solution and/or the suspension that will carry out drying and dehydrating after the active substance component that recycles of wherein existence is purified.
In addition, the interior pressure that is full of the system of steam preferentially is chosen in the normal pressure scope and operates.But particularly preferably be control elevated pressure like this in the recycle system this moment, promptly for example, avoid with can having no doubtful portion occur damaged position-this situation in big industrial setting be may avoid fully never-air invades in the recycle system that is full of steam.
Operation also makes and might turn round with desired high unit time mass flow in the big equipment of industrial product and trouble can not occur in the normal pressure scope.Because external gas, particularly air can not enter in the recycle system that is full of water vapor, therefore avoided secondary damage effectively to the high quality product of making every effort to obtain.Suitable operating pressure for example is can reach about 150 millibars, preferably can reach about 75 millibars, preferably be lower than in the scope of 50 millibars of overvoltages.About 5-10 millibar overvoltage region is ideal.For the present invention, say in principle, use superheat steam drying, can certainly be under negative pressure, particularly under the range of negative pressure of appropriateness, carry out, but in this case, in order to get rid of the damaged position that may occur in the recycle system, with avoid occurring not wishing the air that takes place carve into, just need high tech spending.
In design of the present invention, more vital is to abandon by control optimum drying result in the final product that acts on technological process of hot steam.With regard to described material, can allow residual moisture, also allow the quantity that reaches suitable fully,, just can guarantee that the accumulation and the free-running property of anti-storage of dried material is just passable if can pass through certain " inner dry " these residual water-contents in guaranteeing greatly to form in conjunction with material.
If carry out the temperature sensitivity of exsiccant active substance or active substance mixture and do not require keeping little not considerable moisture content in the main exsiccant product, and in case of necessity in conjunction with graininess and the free-running property of these residual moistures with the anti-storage of assurance dried material, so according to the present invention, use a kind of subsidiary material, this subsidiary material are the fixing special solid matter of moisture preferably.This of residual water-content fixed, and for example can realize by being fixed into crystal water.But similarly, come in conjunction with the limited moisture in the described kind solid matter particle by pure absorption, it is undesirable bonded to one another or to adhere to also be possible not cause therefore that particle occurs.At the subsidiary material that will use sufficient amount like this in such cases at least, although so that exist residual water-content still can guarantee its graininess and anti-storage in the material.
In one embodiment of the invention, after the fresh material that is dried is discharged from nodulizer, be incorporated into immediately wherein, mix then powerfully with suitable manner in conjunction with the subsidiary material of residual water-content.A kind of preferred embodiment in, but these subsidiary material at least partly were mixed in the aqueous solution or the suspension before fluidized bed spray granulation.Exsiccant material temperature susceptibility allows the drying of such scale if desired, so that the residual water-content that is kept can be absorbed fully by these subsidiary material that use together and the bonded words, so top last-mentioned the sort of embodiment is always feasible.
In this regard, of the present invention one preferred embodiment in, use corresponding active substance in stain remover, washing composition and/or the clean-out system field as subsidiary material in conjunction with residual water, they are that temperature is very insensitive.Its typical example is to be selected from the following inorganic active substance that is combined with crystal water: builder component, washing soda and/or so-called suspension stabilizer for example are combined with silicate compound, the especially zeolite of crystal water.At present, an example of expression fabric detergent feature is the zeolite-NaA in the washing composition quality, and it is in conjunction with the ability of calcium in the scope of 100-200mgCaO/g (consult this among DE-2412837 description).Example in conjunction with the washing soda of crystal water is soda or sodium bicarbonate, and quite a large amount of residuary water can be attached on the crystal water as the sodium sulfate of neutral salt or suspension stabilizer.In addition or replace this can be in conjunction with the subsidiary material of crystal water, can also come in conjunction with residual moisture by the auxiliary agent or the corresponding active substance that can absorb moisture.As everyone knows, known burnt hair look inhibitor, fabric softening amendment (particularly based on softening amendment inorganic, silicate that can swelling) based on starch or Mierocrystalline cellulose and a series of be that solid organic surface active agent compound can both receive quite a large amount of moisture under normal condition, and can so and not produce undesirable surface adhesive.
One side is according to the temperature sensitivity of used active substance or active substance mixture, on the other hand according to the character and the quantity of the subsidiary material that use together, in through the exsiccant material, can leave over a considerable amount of residual water-contents and the not graininess of its shelf-stable of induced damage resistive and free-running property.Therefore, the present invention regulation, when carrying out drying with the superheated water vapor, by the residual moisture content in the material of discharging in the fluidized-bed in about 1-20%(weight) time end drying, the optimum range of above-mentioned residual moisture content is about 5-15%(weight).Here said scope is to discharge the weight of material from fluidized-bed.In addition,, be not that the share with the form bonded residual water-content of crystal water preferably is limited in the highest about 10%(weight according to the present invention), particularly be not higher than about 3-4%(weight).Suitable equally here about the explanation of weight percentage above.
The operational condition of the inventive method makes the temperature that can adopt higher circular flow water vapor phase in the drying zone of fluidized-bed.Iff infeeding heat by vapor phase, the working temperature of water vapor phase is suitable especially in about 270-350 ℃ of scope so.Be meant the temperature of supplying with water vapor stream fluidized-bed, that be heated to optimum temps during temperature described here eventually.
Under the situation of the interchanger in employing is arranged on fluidized-bed, heat is mainly introduced by this interchanger.Water vapor is used to form fluidization mutually.In this case, it is lower significantly that the best of water vapor enters temperature, promptly at 150-180 ℃.At this moment, lower rate of drying passes through the length and/or the height of bigger fluidized-bed, thereby the hold-time that prolongs in drying zone is compensated.Therefore, according to the temperature sensitivity of dried material, always there is one to be suitable in these two kinds of embodiments.
Quantitative proportion between the liquid water yield that the further consideration of energetics aspect-particularly will be evaporated about the further utilization of having a mind to that breaks away from the round-robin steam diversion-determined and the feed rate of superheated vapour.Here, following embodiment is feasible, promptly be defined in leave fluidized-bed after vapor temperature limited decline only takes place, and in other embodiment, further utilize the heat energy of water vapor, be reduced near condensing temperature until steam temperature and then conform with purpose.In addition, can also be according to itself being that known mode is divided into different zones with fluidized-bed: high-temperature zone and middle warm area and cooling zone.
One of the present invention is made us interested embodiment regulation especially, reclaim and utilize the heat of condensation of the water vapor part of emitting from working cycle.Adopt suitable operation steps, can guarantee through the hot steam of emitting stream and leave a small amount of active substance of primary steam round-robin and partly realize recirculation.For example can operate under the situation by the described heat of condensation at the vapor portion that utilization is emitted hereinafter this moment:
In a preferred multistage evaporator plant, utilize the heat of condensation of the steam diversion of discharging to put forward dense steam condensate.This moment, resulting residue enriched material was sent back in the elementary technological cycle process.Particularly this enriched material can be added to utilizes the superheated hot steam to want in the exsiccant slurry.
If necessary, when the hot steam condensation of being discharged by initial cycle, necessary words can be supplied with next operation steps with attaching remaining gas phase generation, that be loaded with a small amount of active substance, for example burn, handle in biofilter or in washing plant.Shunt virtually completely recirculation and cancelled last resistates enrichment measure bonded this by each, method of the present invention makes in related career field might be made active substance in washing composition and the clean-out system field or active substance mixture for the first time on a large scale and not produce waste gas and waste water.
In addition or replace to use can be in conjunction with the subsidiary material of resistates moisture, the present invention also stipulated to initial formation, carry out aftertreatment through the part dry granules.Aftertreatment realizes that by two technical schemes these two technical schemes also can combine.
The first string is based on, and the related single degree of drying of each particulate is decided by their granular size.According to the present invention, if at a time interrupted drying process, and also there is quite a large amount of residual water-contents this moment in the material, so the integer of residual moisture content is observed the verity that only has part.The result that the distribution situation of residual water-content in the material each several part observed respectively shows, tiny or the most tiny more precisely part is drying or complete drying to a great extent, and still very moist, thereby can't guarantee the graininess and the free-running property of the shelf-stable of the material of from fluidized-bed, discharging than bulky material part.In the important embodiment of the inventive method, adapt to this situation, realized " follow-up drying " by a postprocessing working procedures additional, one-level at least by the first stage material of discharging in the fluidized-bed, this postprocessing working procedures causes in whole material and the irrelevant homogenizing that has realized moisture content of one granular size, makes the powdered material can be owing to bonding suffers damage.Adopt this method that the also relatively moist thicker part of considerable residual water-content from material transferred in tiny and the fine material, thereby after this homogenizing operation, guaranteed the graininess and the free-running property of the shelf-stable of dried material, discharged other moisture and need not from this particulate materials, add.
All make in each particle moisture content reach unanimity and can prevent that material agglutinating processing method is even and regular simultaneously and be used for above-mentioned postprocessing working procedures.Here only exemplarily point out severally, promptly the material that first product forms is rotated, stirs or vibrates with successive or mode intermittently.Suitable especially is in additional another fluidized-bed that connects material to be carried out aftertreatment.
In this case, use arbitrary gas, preferably operate with ambient air.At this moment, the oxidative damage of material and undesirable exhaust emission all can or can not take place, and be easy to be controlled hardly.Owing to will carry out the exsiccant material from having comparatively high temps, normally in the fluidized-bed of about 105 ℃ of scopes, discharge, therefore handle and can also further reduce residual moisture slightly by in fluidized-bed, carrying out this additional moisture homogenizing.
In addition or replace this assist measure, but can also take one or more levels additional drying in the method for the invention, reduce remaining moisture with further.This follow-up exsiccant feature is to operate under the condition of the active substance that does not damage dried material.As the example that is intended to reduce dangerous processing parameter, that can point out has: the temperature that reduces hot phase; Do not use superheated vapour to replace the dry gas in other source, for example air and/or rare gas element as hot gas; And change a kind of other drying process over to.
The method that bed spray is granulated is to be based upon on the basis of core growth, these cores in fluidized-bed by do not meet, the solidified spray droplets forms, or broken generation of solid particulate grinding by having existed already, perhaps also can be to deliver in the fluidized-bed by the outside.Can carry out the granulation condition that must remain unchanged continuously in order to guarantee technological process.All all must be quantitatively by new core compensation by the particle of discharging in the fluidized-bed.On the other hand, must from waste gas, remove the tiny material part of carrying together.These tiny particles also can be used as the core material.In order to guarantee above-mentioned particulate compensation in a kind of not only simple but also economic especially mode, suggestion will partly be separated with the tiny material that waste gas leaves fluidized-bed, especially inside is sent it in fluidized-bed back to by means of a dust-collecting filter that is provided with above fluidized-bed, is used as to form the particulate core.Also can finish by isolating tiny material in the waste gas with whirlwind separator.But, advantageously utilize the lid that is arranged on nodulizer cloth envelop collector interior and that be configured in above the fluidized-bed to clear up waste gas.In any case partly send back in the fluidized-bed in all necessary waste gas cleaning with thin material with this, can save the space.
In order only those particles that reach the particle size that requires to be discharged from fluidized-bed, suggestion makes particle pass through one or more separators by discharging in the fluidized-bed in a structural arrangement that further enlarges.These separators advantageously are arranged in the air inlet bottom of fluidizer to save the spatial mode.It would be desirable and adopt the adverse current gravity separator.
Some stain removers, washing composition and/or the active substance of clean-out system and the moisture preparation of active substance mixture especially like this that are suitable for using in the method for the invention, promptly they can or can not suffer damage after the short period of time shock action of water that passes through 100-120 ℃ of temperature of charge scope or water vapor basically.The component of following kind is especially suitable for use as the active substance composition, and promptly they can stand said temperature and reach 5 seconds to 5 minutes clock times at least and unlikely suffering damage under working conditions.It is essential, in the method for the invention the time of said temperature effect so short, therefore under selected working conditions, to carry out the exsiccant material and substantial infringement also not occur.If abide by the regulations, be the known environment condition to affiliated technical professional, so for example itself there is the surface active cpd of hydrolysis danger under such working conditions, can stand the residence time of several seconds, and can be subjected to damaging significantly to several minutes.In drying means of the present invention, the moisture preparation of the water soluble of stain remover, washing composition and/or clean-out system and/or water-fast, organic and/or inorganic active substance can withstand drying, and described active substance for example can be enumerated following substance classes: the component with Action of Surfactant or emulsifying agent effect; Inorganic and/or organic matrix or builder component; Washing soda; Suspension stabilizer or neutral salt; Fabric softening amendment; Bleach activator; Be used to improve the auxiliary agent that carries the foul ability of dye liquor, for example burnt hair look inhibitor; Perhaps also has abrasive.
In an important embodiment, the drying means of active substance mixture of the present invention is used to make fabric detergent.Carry out containing tensio-active agent and matrix or builder material in the aqueous material of packing into of exsiccant, also contain washing soda and/or neutral salt as required with detergent active.Wherein, have at least in the employed multicomponent mixture part can in conjunction with and/or fixing residual moisture, particularly with the form of crystal water.As in the spray drying process of fabric detergent, under the situation of this substance mixture, fabric detergent is not all to stand fluidized bed spray granulation with it in general.Contain superoxide bleaching components (as perborate-hydrate or tetrahydrate) the extreme temperature sensitivity and do other does not allow the responsive especially component of temperature accordingly.As other example, can also enumerate enzyme, spices, bleach-activating agent and other accessory constituent.Instruction corresponding therewith of the present invention in addition also stipulates to make so-called polycomponent tower powder, and it has the most of component that constitutes the finished product washing composition concurrently, but after this adds or mix other liquid and/or solid active substance component again.The example of known this class I liquid I component is the component of volatile especially nonionogenic tenside (niotensidisch), although this in the method for the invention component no longer is discharged in the surrounding environment by waste gas, it is joined be still in the whole washing composition by what realize on the additional particle that is sprayed to by the previously prepared suction of the present invention, this practice is comparatively easy.
Explanation utilizes principle of work of the present invention that active substance is used to make stain remover, washing composition and/or clean-out system directly or indirectly prevailingly below, has also described the component of fabric detergent commonly used at present simultaneously.
As anion surfactant, for example can use by natural or synthetic, the soap that obtains of saturated fatty acid preferably.Particularly suitable be the soap mixture of deriving and obtaining by natural acid such as coco-nut oil fatty acid, palm kernel fatty acid or stearic acid.It would be desirable saturated C by 50-100%
12-18The mixture that the oleic acid fatty acid soaps of fatty acid soaps and 0-50% constitutes.
In addition, the synthetic anion surfactant of Shi Yonging is the tensio-active agent of sulfonate and vitriol type.Thus, method of the present invention has the meaning of particularly important for the respective compound that derives from plant and/or animal.
As the tensio-active agent of sulfonate type, can consider with alkylbenzene sulfonate (C
9-15Alkyl), hydrocarbon belong to sulfonate (promptly by alkene-and the mixture that constitutes of hydroxyl sulfonated alkane) and sulfonate, they for example can be by having the C that is positioned at end or inner two keys
12-18Monoolefine with gaseous sulfur dioxide carry out sulfonation, then with sulfonated products basic hydrolysis or acid hydrolysis and make.(they can make the sulfonated alkane that also has that is fit to use as follows: by C
12-18Alkane is through sulfochlorination or sulfoxidation, with posthydrolysis or neutralization, perhaps by alkene is carried out the hydrosulphite addition) and the especially ester of alpha-sulfo-fatty acid (Estersulfonate), for example hydrogenant fatty acid distribution of coconut oil, palm kernel fatty acid or stearic α-sulfonated methyl esters.
In this regard, important surfactivity or emulsifier component also have so-called double salt, and it can make by the saponification of above-mentioned α-sulfonated fatty acid methyl ester, perhaps also can be by specific saturated fatty acid (C especially
12-18Lipid acid) Direct Sulfonation prepares.
The tensio-active agent of the vitriol type that is suitable for has by natural or synthetic primary alconol (being Fatty Alcohol(C12-C14 and C12-C18) such as coconut lipidol, stearyl alcohol, oleyl alcohol, lauryl alcohol, tetradecyl alcohol, palmityl alcohol or Stearyl alcohol) or C
10-20Carbonyl closes the sulfuric acid monoester that face secondary alcohol pure and this chain length obtains.The component that is suitable for also has natural and/or synthetic, with the sulfuric acid monoester of the alcohol of 1-6 moles of ethylene oxide ethoxylation.As the example of synthol, can enumerate the C of the 2-methyl branch that for example has average 3.5 moles of ethylene oxide
9-11Alcohol.In addition, Sulfated lipid acid monoglyceride also is suitable for.
Anion surfactant can exist with the form of sodium salt, sylvite and ammonium salt, and perhaps the form with the soluble salt of organic bases exists.
As nonionogenic tenside, can use preferably 2-20 of 1-40() moles of ethylene oxide and 1 mole has adduct 10-20 carbon atom, that be selected from the aliphatic cpd of alcohol, carboxylic acid, fat family amine, hydrocarbon acid amides or alkane sulfonamide basically.Particularly importantly 8-20 moles of ethylene oxide and primary alconol (as coconut lipidol or stearyl alcohol), oleyl alcohol, oxo alcohol or with have preferably 12-18 of 8-18() adduct of the secondary alcohol of individual C atom.Except water soluble nonionic surfactant, the polyglycol ether that has the insoluble of 2-7 ethylene glycol ether in the molecule or not exclusively be dissolved in water also is significant, especially when they use with water miscible, nonionic or anion surfactant.In the method for the invention, owing to following reason will be considered the trend of carrying of this nonionogenic tenside, promptly this class component is granulated in bed spray and completely or partially is applied on the resulting granules after finishing.This is effective especially for the nonionogenic tenside (Niotenside) that at room temperature is liquid.
In addition, nonionogenic tenside can also use general formula to be R-O-(G) the alkane glycosides (Alkyglykoside) of x, R represents that has a preferably 12-18 of 8-22(in the formula) aliphatic group of the elementary straight or branched of individual carbon atom, G is a symbol, it represents a glucose unit with 5 or 6 carbon atoms, and oligomeric degree x is between 1 and 10.
What be suitable as organic and inorganic matrix or builder material is the solubility and/or the insoluble component of super faintly acid, neutral or alkali reaction, they can the precipitated calcium ion or can complexing combination.The builder material that is suitable for and especially do not cause ecological aspect problem is the synthetic zeolite of the fine crystallization of mentioned kind.Can consider (being total to) polymeric polycarboxylate with other builder component that zeolite uses, for example polyacrylic ester, polymethacrylate, and the multipolymer of vinylformic acid and toxilic acid especially are preferably with the multipolymer of 50% to 10% toxilic acid.The molecular weight of homopolymer generally is between 1000 and 100000, and the molecular weight of multipolymer mainly is between the 50000-120000 between 2000-200000, and is relevant with free acid.A kind of molecular weight of particularly preferred vinylformic acid-maleic acid is 50000 to 100000.Although be suitable for using also-be less preferential selection in this compounds-acrylic or methacrylic acid and vinyl ether vinyl for example.The multipolymer of methyl ether, wherein acid moieties reaches 50% at least.In addition, can also use polymeric acetal carboxylate, as described in United States Patent (USP) 4144226 and 4146495, and use polymeric acid, these acid can be by with the propenal polymerization and then utilize alkali to make it disproportionation manufacturing, also can be made of acrylic acid units and vinyl alcohol units or propenal unit.
Operable organic substrate for example has the poly carboxylic acid that preferably uses with its sodium-salt form, as citric acid and nitrilotriacetate (NTA), as long as use them not scolded because of the reason of ecological aspect.
Allowing to contain under the phosphatic situation, also can use phosphoric acid salt simultaneously, especially Thermphos SPR (Pentanatriumtriphosphat) if possible also has pyrophosphate salt and orthophosphoric acid salt, and they mainly are as precipitation agent calcium salt to be had an effect.
The salt inorganic, that do not form complex compound that is suitable for is alkali-metal supercarbonate, carbonate, borate or silicate, and they are also referred to as " washing soda "; In alkalimetal silicate, particularly suitable be Na
2O: SiO
2Ratio be 1: 1 to 1: 3.5 water glass.In all the other components of conventional washing composition matrix, can consider the specific components that is selected from burnt hair look inhibitor (dirt carrying agent), neutral salt and fabric softening amendment in addition that uses together in the method for the invention.
The burnt hair look inhibitor that is suitable for for example has carboxymethyl cellulose, methylcellulose gum, methyl hydroxyethylcellulose and their mixture, as the example of the representational neutral salt that is suitable for, the sodium sulfate of having mentioned above can enumerating.The softening amendment that is suitable for for example is the layer silicate of the energy swelling of corresponding montmorillonite kind, for example wilkinite.
With the clean-out system of washing composition commonly used, to the mixing element of high temp. sensitive, for example based on the SYNTHETIC OPTICAL WHITNER of superoxide, be selected from the enzyme of proteolytic enzyme, fat ester and amylase etc., bacterial strain or fungi, stablizer, spices, thermally sensitive staining agent or the like mixes with the particle that obtains in advance mutually according to the favourable mode of having described.
Below, the embodiment and the test-results of the inventive method are described in further detail.
Testing apparatus represented in Fig. 1 summary.This device is mainly by forming with the lower section: a vortex combustion chamber 1, it has one and is divided into seam formula bottom 2 two parts, that can distinguish air inlet, one is used for the impeller gate 3 that product is discharged, with a tube-bundle heat exchanger 4 that is arranged in the vortex combustion chamber 1, it is positioned at the top of seam formula bottom 2.The screw transfer roller 5 that has batch meter 6 is used for sending back to ground and crosses coarse particles.Dried material, i.e. slurry by being pumped into the charging nozzle through pipeline 7 in the heated container, is injectedly gone in the fluidized-bed.
During on-test, put into so-called " tower powder " (Turmpulver) as the fluidized-bed working medium.It is to utilize warm air to adopt (the bulk density 550g/l for preparing in the traditional drying method type of production spraying type washing tower.Residual moisture about 12%).This tower powder contains the 16%(weight of having an appointment) tensio-active agent, 15%(weight) soda, 28% zeolite NaA, about 2% water glass, Sokalan(R) and submember commonly used.
After making the boiling material form fluidization with warm air, spray into detergent slurries (about 30kg/h, spraying pressure 6 clings to) by feed nozzle (aperture 0.7mm).Its solid phase partly contains component recited above.
The initial water content of above-mentioned slurries is 50%.A moist waste gas part is discharged from, and major part is circular flow still, and wherein the airflow of circular flow is reheated in the heat exchanger 9 of fluidized-bed front.The airflow of discharging is compensated again by fresh air.The temperature of air is about 145 ℃ when entering fluidized-bed, is about 90 ℃ in the exit air themperature.
In the formed particle, a part is discharged, is ground broken in by fluidized-bed and infeed again in the fluidized-bed as the particulate core by screw hauler 5 through impeller gate 3.The time that product stops in fluidized-bed is about 20 minutes.
After determining that through the observation of several hrs bulk density no longer increases, use superheated vapour instead and carry out drying.Situation when using air before this is the same, and steam also is circular flow.The overheated of steam is to realize by interchanger 9 that is positioned at the fluidized-bed front and the tube-bundle heat exchanger 4 that is arranged on fluidized-bed again.The temperature-averaging that enters of steam is 150 ℃, is 105 ℃ in the temperature of the exit of fluidized-bed steam.The flow of slurries is 30kg/h.When steam drying begins, receive thing before using the particle that in the back test, produces as bed by dry air.About altogether 20 minutes of the time that this product is detained in fluidized-bed.
Test-results is shown in table 1 and the table 2.
Provided three kinds of bulk densities in the table 1 by the sample of discharging in the fluidized-bed:
Table .1
Sample 367
Recycle gas air vapor steam
Inlet air temperature (℃) 140 150 152
Exhaust temperature (℃) 100 108 108
Gas flow (operation) 635 940 945
Flow m
3/ h)
Productivity (kg/h) 30 30 30
TS enters (weight %) 50 50 50
TS discharges (weight %) 94.3 94.9 94.3
Bulk density (g/h) 687 780 820
The TS-dry-matter content
Find that through observing bulk density has improved significantly, sample 3 is 687g/l, and sample 6 surpasses 782g/l, and sample 7 then is increased to 820g/l.In all cases, residual moisture all is about 5% (measuring in 7 minutes with ultra red ray drying at 135 ℃).
Sizing analysis result (seeing Table 2) shows that particle becomes thicker during with steam drying.
Photo with the optics microscope photographing shows, compares the smoother and evenly significantly on particulate surface when the dry air with steam drying.The photo that granule interior is taken shows, compares with steam drying, and is few and little with pore in air dried particle.Consequently, the particulate solvability with steam drying has improved significantly.
In addition, do not observe owing to the pipe of heat exchanger directly contacts on the interchanger 4 that sticks in the fluidized bed and product suffers damage situation.
Table 2: sizing analysis
Sample 367
Greater than 1.6mm 9.8 46.5 31.4
Greater than 0.8mm 46.9 43.3 56.7
Greater than 0.4mm 27.6 8.3 10.9
Greater than 0.2mm 8.9 1.3 0.8
Greater than 0.1mm 3.4 0.5 0.3
Less than/equal 0.1mm 3.5 0.2 0.2
The reference symbol table
1. vortex combustion chamber
2. stitch formula bottom (air inlet bottom)
3. impeller gate
4. heat exchanger
5. screw transfer roller
6. batch meter
7. pipeline
8. gas blower
9. heat exchanger
10. flow measurement and control device
11. whirlwind separator
12. gas blower
13. excess steam
14. junctor
Claims (25)
1; in the normal pressure scope and in the fluidizing agent of heat; granulate by being suitable as stain remover by bed spray; washing composition and/or clean-out system and/or person are suitable for the aqueous solution of active substance in these preparations or active substance mixture and/or the pine dress that suspension is made described active substance or its mixture continuously or the method for discrete particle; it is characterized in that; use superheated vapour to operate as fluidizing agent; before particle suffers damage because of the effect of heat, it is discharged from nodulizer during operation; can guarantee above-mentioned graininess and free-running property of passing through the anti-storage of part exsiccant material in conjunction with the component of mixture of the confined water yield and/or by aftertreatment by adding in case of necessity; in addition; operation is to carry out in a closed system with water vapor circulating current; the transpiring moisture of extracting the material of packing into out from this system is supplied with this system as shunting again with liberated heat.
2, the described method of claim 1 is characterized in that, do not weigh by being located at the heat exchanger in the fluidized-bed, but also by being located at outside heat exchanger to the hot steam heat supplied.
3, the described method of claim 1, it is characterized in that, when the responsive especially active substance of heat or its mixture are carried out drying, only by outside heat exchanger to the hot steam heat supplied, residence time this moment control when in fluidized-bed, heat exchanger being set weak point.
4, each described method in the claim 1 to 3 is characterized in that, the material of wherein carrying secretly of packing into is removed in the shunting that will extract out from the water vapor circulating current, and is used as technological process steam in addition.
5, each described method in the claim 1 to 4, it is characterized in that, to major general's part by the shunting condensation of extracting out in the water vapor circulating current, with wherein contained active substance, in case of necessity carry in advance dense after, be used for the preparation to carry out the exsiccant aqueous solution and/or suspension.
6, each described method in the claim 1 to 5, it is characterized in that, the interior pressure that is full of the system of steam is in the normal pressure scope, but preferably operate under a kind of like this elevated pressure this moment, thereby avoided air to invade in this system, when operation, pressed preferably below about 50 millibars malleation in the system at for example damaged position.
7, each described method in the claim 1 to 6, it is characterized in that, use subsidiary material to be combined in contained residual water-content in the product of complete drying not at least in part, thereby guarantee the graininess and the free-running property of the shelf-stable of dried material, these subsidiary material at least partly were mixed in the aqueous solution or the suspension before bed spray is granulated.
8, the described method of claim 7 is characterized in that, uses stain remover, washing composition or clean-out system component, particularly washing assistant, washing soda and/or suspension stabilizer as the subsidiary material that are used in conjunction with residual water-content.
9, each described method in the claim 1 to 8, it is characterized in that, when in fluidized-bed, carrying out drying with superheated vapour, when residual moisture content in about 1-20%(weight), particularly in about 5-15%(weight) in the scope time, interrupt this drying process, this moment preferably with free, be not to be limited in the highest about 10%(weight with crystal water form bonded water-content) numerical value, this is that weight with the material of discharging from fluidized-bed at that time is basic calculation.
10, each described method in the claim 1 to 9 wherein only infeeds heat by vapor phase, it is characterized in that, uses the fluidizing agent of the water vapor of about 270-350 ℃ of inlet air temperature as fluidized-bed.
11, each described method in the claim 1 to 9 wherein additionally infeeds heat by the heat exchanger that is arranged in the fluidized-bed, it is characterized in that the inlet air temperature of water vapor is at 150-180 ℃.
12, the described method of claim 16 is characterized in that, the material component that is partly reclaimed and preferentially unload in the heat of condensation of the steam of drawing to the major general sends back under the situation of initial cycle, and essentially no waste gas and waste water ground are operated.
13, the described method of claim 1 to 12 is characterized in that, makes gained particulate residual moisture content homogenizing in having the postprocessing working procedures of one-level at least.
14, the described method of claim 13 is characterized in that, as fluidizing agent, makes the residual moisture homogenizing with air in another fluidized-bed.
15, each described method in the claim 1 to 10 is characterized in that, under the condition of protection active substance the particle that also contains residual water-content is carried out sintering and follow-up drying or aftertreatment.
16, each described method in the claim 1 to 11, it is characterized in that, isolate the subparticle material that leaves fluidized-bed with waste gas, especially inside sends back to it in fluidized-bed by means of a dust filter that is arranged on the fluidized-bed top, as being used for forming the particulate core.
17, the described method of claim 16 is characterized in that, utilizes in the top be arranged on nodulizer and the cloth envelop collector that is positioned at above the fluidized-bed is cleared up waste gas.
18, each described method in the claim 1 to 17 is characterized in that, by one or more, particularly be located at separator in the air inlet bottom of fluidizer, adverse current gravity separator preferably, with particle by discharging in the fluidized-bed.
19, each described method in the claim 1 to 18, it is characterized in that, use the moisture preparation of more such active substances or active substance composition, described active substance or its composition can be owing to effect do not suffer damage in the short period of time of the water and steam of 100-120 ℃ of temperature range, and with the temperature that employed preparation form can stand above-mentioned scope reach 5 seconds at least-5 fens clock times unlikely suffering damage.
20, each described method in the claim 1 to 19, it is characterized in that, moisture preparation to following material is implemented this method: the active substance of water soluble and/or water-fast, organic and/or inorganic, stain remover, washing composition and/or clean-out system, as have the component of tensio-active agent or emulsifying agent effect; Inorganic and/or organic matrix or builder component; Washing soda; Suspension stabilizer or neutral salt; Fabric softening amendment; Bleach activator; Be used to improve the auxiliary that carries the dirt ability, as burnt hair look inhibitor; And abrasive.
21, each described method in the claim 1 to 20, it is characterized in that, in tensio-active agent or emulsifying agent or matrix or auxiliary agent agent, particularly obtain the one-component as the active substance selection of organic or inorganic character with the form of loose dried material by the active substance scope that is used for fabric detergent.
22, each described method in the claim 1 to 21, it is characterized in that, drying is used to constitute the active substance mixture of fabric detergent, it contains tensio-active agent and matrix or builder material, necessary words also contain washing soda and/or neutral salt, have at least in the wherein multi-component mixture a part of component can in conjunction with and/or fixing residual water-content.
23, each described method in the claim 1 to 22, be used to prepare loose solid surfactant material, particularly based on the anion surfactant of crude substance, it particularly is present in the mixture that forms with the soluble inorganic salt that is used for guaranteeing free-running property and/or bulk density.
24, each described method in the claim 1 to 22, be used to make exsiccant active substance based on silicate, they can be applicable in the fabric detergent especially, and in the washing composition quality, comprise corresponding representational silicate can swelling and/or can not swelling, as layer silicate and/or zeolite compound, zeolite NaA particularly.
25, each described method in the claim 1 to 22 is used to make fabric detergent tower powder, to wherein mixing temperature sensitive and/or the volatile component of water vapor, to form the finished product fabric detergent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93101453 CN1076721A (en) | 1993-02-11 | 1993-02-11 | Be suitable as the particulate manufacture method of stain remover, washing composition and/or clean-out system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93101453 CN1076721A (en) | 1993-02-11 | 1993-02-11 | Be suitable as the particulate manufacture method of stain remover, washing composition and/or clean-out system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1076721A true CN1076721A (en) | 1993-09-29 |
Family
ID=4983600
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93101453 Pending CN1076721A (en) | 1993-02-11 | 1993-02-11 | Be suitable as the particulate manufacture method of stain remover, washing composition and/or clean-out system |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1111594C (en) * | 1993-11-02 | 2003-06-18 | 尤尼利弗公司 | Make the method for detergent composition |
| CN105377032A (en) * | 2013-07-11 | 2016-03-02 | 阿格洛法士公司 | Methods and compositions of granule formulations |
| CN107869887A (en) * | 2016-09-27 | 2018-04-03 | 梁振冬 | One kind vortex drying tower |
| CN109382039A (en) * | 2018-12-11 | 2019-02-26 | 盐城市大明化工机械有限公司 | Vacuum spraying fluidisation granulator |
| CN110198778A (en) * | 2017-01-25 | 2019-09-03 | 蒂森克虏伯工业解决方案股份公司 | Method and apparatus for carrying out recuperation of heat in fluidized bed prilling |
| CN113444584A (en) * | 2021-06-25 | 2021-09-28 | 山东新华莎罗雅生物技术有限公司 | Solid enzyme cleaning agent and preparation method thereof |
-
1993
- 1993-02-11 CN CN 93101453 patent/CN1076721A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1111594C (en) * | 1993-11-02 | 2003-06-18 | 尤尼利弗公司 | Make the method for detergent composition |
| CN105377032A (en) * | 2013-07-11 | 2016-03-02 | 阿格洛法士公司 | Methods and compositions of granule formulations |
| CN107869887A (en) * | 2016-09-27 | 2018-04-03 | 梁振冬 | One kind vortex drying tower |
| CN110198778A (en) * | 2017-01-25 | 2019-09-03 | 蒂森克虏伯工业解决方案股份公司 | Method and apparatus for carrying out recuperation of heat in fluidized bed prilling |
| CN109382039A (en) * | 2018-12-11 | 2019-02-26 | 盐城市大明化工机械有限公司 | Vacuum spraying fluidisation granulator |
| CN113444584A (en) * | 2021-06-25 | 2021-09-28 | 山东新华莎罗雅生物技术有限公司 | Solid enzyme cleaning agent and preparation method thereof |
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