CN100354029C - Method for reducing exhaust carbon dioxide - Google Patents

Abstract

A method for effectively absorbing and removing CO2 in an exhaust gas generated during an industrial process for reducing the amount of CO2 that is exhausted into the atmosphere. The exhaust gas containing CO2 is blown into an agglomerate of solid particles containing CaO and/or Ca(OH)2 so that the CO2 is in contact with the agglomerate for fixing the CO2 in the exhaust gas as CaCO3, thereby reducing the CO2 concentration in the exhaust gas. Preferably, the solid particles contain water, and more preferably, the solid particles contain surface adhesive water.

Description

Bulk material and the production method thereof of a kind of sinking in water

The application is that the application number submitted on October 28th, 1999 is 99812077.4, denomination of invention is divided an application for the application for a patent for invention of " reducing the method for the carbon dioxide gas of discharging ".

Technical field

The present invention relates to reduce the CO in the emission gases that produces in the industrial processes ₂Concentration, minimizing CO ₂The method of the discharge capacity in atmosphere.What the invention still further relates to usefulness such as algae field, fishing bank and riverbed heavyly is located at stone material in the water and their manufacture method thereof, and the method for building the algae field.Above-mentioned so-called " algae field " is meant the group bottom culture seaweeds (algae, sea grass etc.).

Background technology

From preventing the viewpoint of global warming, appeal to reduce CO in the world in recent years ₂Growing amount, hold in the capital of a country in December, 1997 prevents the global warming meeting, has passed through in meeting about reducing the protocol of emission gases.In this protocol, stipulate: at the gas (CO of all industrial advanced country generation greenhouse effects in 2010 ₂, CH ₄, N ₂O etc.) discharge capacity reduces 5% than the level of nineteen ninety at least, so China has born the obligation of gas emissions minimizing 6%.

Press contribution, CO to the greenhouse gases kind of global warming ₂Influence degree account for 64%, mainly be to use fossil fuel discharging.Is CO in China in the greenhouse gases 95% that society, economic activity produce ₂, and think it wherein is to follow the use of energy to produce more than 90%.Therefore as preventing the global warming countermeasure, follow energy to use the CO that produces with inhibition ₂Discharging be the center.

Follow energy to use the CO that produces about suppressing ₂Discharging, for example account for China's final energy and consume about 11% steel industry, formulated towards 2010 from master game plan, propose in the works at this: reduce 10% than nineteen ninety at production process energy consumptions in 2010.In addition as its concrete matching strategy, propose except that reducing energy uses, waste plastics as reducing agent to blast furnace blowing and the correct use in the neighbour area that does not utilize energy, utilize goods and byproduct society to energy-conservation contribution etc.

In the society of modern intense industrialization, the use that suppresses energy is and reduces CO ₂Discharging is associated, and is limited but suppress the energy use, only will reach with the use that suppresses energy and reduce CO ₂The discharging purpose may not be easy.

Therefore suppress CO in order to reach ₂The purpose of discharging is reducing CO ₂Growing amount the time to remove CO in the gas (gas of discharging) of generation ₂, think that it is necessary starting with from two aspects.Do not grasp plant-scale all the time and can effectively remove CO in the emission gases ₂Method.

Mention technical background, for seeking effectively to utilize the slag that produces in the steel manufacture process, attempted slag is utilized at marine material with sinkings such as stone material and fishing banks as the algae field in the past.

Under the situation of slag as above material use, think principal mode be block slag directly as the method for the stone material of usefulness such as algae field, and the method for utilizing as the aggregate of concrete fishing bank etc.There is following problem in these methods.

At first in preceding a kind of method, the Ca part that contains in slag is molten in seawater, and worry can make the pH value rising of seawater on every side.In addition, the block slag of the reset condition that obtains in the steel manufacture process, wait from its surperficial proterties, compare the stone material that is suitable for doing usefulness such as algae field with concrete product, block slag only has and lithotome identical functions (tack of seaweeds, breed property) as the stone material of usefulness such as algae field, rather than the stone material with the specific function that can promote that seaweeds is cultured.

In addition, the slag that produces in the steel manufacture process contains the composition of a large amount of iron blocks iron such as (granular irons), so generally will be broken into to a certain degree size to slag, reclaims the iron that is contained in the slag and turns back in the steel manufacture process.The slag as the stone material of usefulness such as algae field need have the dimensions, and almost can not use for reclaiming the slag that iron block carries out break process.When using as the stone material of usefulness such as algae field, may reclaim the iron block that use value is arranged as ferrous materials hardly for this block slag.

On the other hand above-mentioned when containing the many block slags of iron block and intactly sinking to marine stone material and use as usefulness such as algae fields, the oxidation of iron causes seawater oxygen deprivation on every side in the marine site of using can be because of slag, has because the dissolving of iron provides the composition of excessive iron sometimes in seawater again.In order to avoid such problem, must fully remove the iron block in the slag, but general slag composition and iron block are interweaved and mix, so will fully remove iron block must be thinner must be than above-mentioned recovery iron block the time the slag fragmentation, and the slag that is broken carefully like this can not use as the heavy material of establishing marine usefulness such as algae field fully.

In addition, a kind of method in back is owing to be that the aggregate of slag as concrete precast block used, so be not easy to produce block slag remained untouched and sink to problem when marine, the material that obtains with the method is that the surface is the concrete product of cement mortar, so wait to use as the algae field and think that the proterties (for example concavo-convex surface texture etc.) that connects block slag can not effectively utilize, just can not expect that also it can reach such performance.

In recent years to the natural environment in river, comprise the living environment that fish and shell-fish etc. are biological, the chance of renovating and improving increases, as a ring wherein, for example attempt existence and the breeding that becomes to help organism in water (fish, shell-fish, aquatic insect etc.) and water plant (algae, pasture and water etc.) repaired in the riverbed.Therefore the biological existence, the resting space that are called as so-called life space (biotopes) in the river are that the stone of effluent bed causes mostly, we can say generally that the concavo-convex many riverbeds that cause because of stone etc. are the easy survival environment of organism in water.The bigger space between the bulk stone under water or that surface in the river for example, and the little space between the small stone of place mat in the riverbed all are important life spaces for organism in water.The stone in riverbed also is the place of water plant such as algae breeding, also is important in order to make the water plant breeding that stone be arranged.

Therefore as a ring of renovating and improve the natural environment in river, when reconstruction riverbed etc., on the riverbed with suitable form sinking or place mat stone material (for example the bulk stone material view and admire stone, the middle piece of sinking place mat and fritter stone material etc. in the riverbed), renovate the environment of existence of organisms in water such as becoming to help fish and water plant and breeding, become effective means.The reconstruction riverbed needs a large amount of stone materials like this, raise the natural stone material that needs usefulness in other places, can worry to cause the problem of new breaking-up nature again, and natural in addition stone material itself is not cheap, and construction cost can increase.

In recent years, as a kind of approach of trying hard to effectively utilize the slag that produces in the steel manufacture process, attempt to utilize slag to do the material of sinking at marine fishing bank.Therefore also can consider the slag that produces in this steel manufacture process as the stone material of sinking in the river.

When slag was used as the stone material of sinking in the river, main form was the method for directly block slag being utilized as the stone material of sinking, and the method for making the aggregate of concrete precast block with slag.

There is following problem in these methods.

In first method, Ca composition contained in the slag is dissolved in the water, and worry can make the pH value of water in the river raise.Because the slag that produces in the steel manufacture process contains a large amount of iron blocks (granular iron), granular iron was wanted oxidation when the direct submerged of block slag used in addition, and worry can cause the river oxygen deprivation around the waters.For fear of the necessary iron block of fully removing in the slag of such problem takes place, but general slag and iron block mix with being interweaved, so will fully remove iron block must be very carefully broken slag, the slag that is broken carefully like this can not be used as the stone material that sinking is used again in the river.

In a kind of method in back, when slag is used as the aggregate of concrete precast block,, use, can not effectively utilize the proterties (for example concavo-convex surface texture etc.) of the slag of anticipation as the stone material of sinking in the river owing to be concrete product basically.Concrete pH value high (the general pH value is about 12～12.5) has, owing to also can be worried to occur the pH value rising of river on every side, or produce the problem that delays algae reproduction again.

In recent years, recognize fish vacillate up and down moving and upstream fish pass will be set in the dam built and the weir dike etc. that various places are also in the transformation of carrying out dam and weir dike etc. for this reason on the river.Fish pass is that the part of dam and weir dike forms the water route (be generally and have wide water route, 2～5m left and right sides) that the current can allow fish move form, and that has known has modes such as tilting, staged.General in the past fish pass was incision such as the part of dam and weir dike etc., the water route that fences up with concrete walls.

This in the past fish pass does not have any problem special, that become restriction fish moving disorder at the flow velocity of water, the inclination of bottom, the aspects such as the discrepancy in elevation of step.Because the fish pass of concrete system bottom is level and smooth, water plants such as algae are difficult for breeding, creep on the riverbed (surface of projections such as stone and water plant) to being hooked in, or hook the organism in water (for example shell-fish and aquatic insect etc.) of moving in the riverbed in the fast place of current with pawl etc. and have the problem that moves difficulty with pawl etc.For such problem, the employing foamed concrete that has is made fish pass, forms the method for micro concavo-convex in the bottom of fish pass, such fish pass construction cost height, poor practicability.But it is all high no matter how to do concrete pH value, does not wish it is the fish pass of concrete system for the organism in water that bed along the river moves.

We can say that the algae field is that the coastal region produces marine vegeto-animal place, as indispensable places such as the growth place of the spawning place of life area, fish and Jie's class of useful fish, Jie's class and seaweeds, juvenile fish and feed places.Also paying close attention to the effect that the algae field purifies water recently, marine alga draws nitrogen and the phosphorus in the seawater, or is drawn by other biological by food chain and to be removed, and algae field inner suspension material precipitate removal etc. from water.

Influenced by the littoral landfill and the pollution of seawater etc., the algae field constantly disappears rapidly and fails, and particularly occurs being called as the phenomenon of " red tide " recently in a lot of coastal marine sites, becomes very big problem.Seeking to establish as early as possible the method for building the algae field, to recover the algae field for this reason.

The construction algae field method of Cai Yonging had two kinds of methods from big aspect branch in the past.

(1) sets up in the place of wanting to build the algae field and support the basement rock (mainly being stone materials such as lithotome and concrete precast block) of planting seaweeds, the seedling of seaweeds and female algae are transplanted on this basement rock, necessary management is carried out in the growth of seaweeds.

(2) in place with the easy growing environment of marine alga, that is to say that environment aspects such as being selected in the depth of water, water quality, ocean current is fit to do the algae field, and the place in the scope that the sporozoite etc. of seaweeds can arrive from existing algae field, basement rock is set, builds the algae field with supporting the method plant (that is to say the transplanting of not carrying out seedling etc. basically and to their growth management) naturally.

In these methods, method (1) has the wide advantage of range of choice, building the algae field is that the people carries out basically entirely, and will be according to the environment of algae field construction site, must to the seedling transplanted survive and growth is managed fully, to spend a large amount of labours and expense for this reason, be not suitable for building on a large scale the algae field.

On the other hand, method (2) owing to be plant the method for building the algae field with supporting naturally, compared with method (1) and is had the labour and cost all will reduce a lot of advantages except that basement rock is set, but owing to build the local limited of algae field, so the shortage generality.Introduce according to a report, the place that does not have nature to form the algae field to use method (2) during suitable in construction algae field, consider from existing algae field energy to make the sporozoite of seaweeds and the scope that seed arrives, preferably be selected in existing algae field 100m with interior place.Therefore think that it is difficult building the algae field with the method place that whole algaes field, marine site disappears around so-called red tide.

Technical scheme

Therefore in view of such present situation, the 1st purpose of the present invention is: the CO in a kind of emission gases that can effectively absorb and remove the industrial process generation is provided ₂, reduce CO ₂The method of the discharge capacity in atmosphere.

The inventor finds can be plant-scale, and effectively absorb and remove CO in the emission gases ₂Method, to CO ₂Absorbing material and using method carried out detailed research, found that such solid particle aggregates that contain CaO such as slag and concrete, as CO ₂Absorbing material be optimum, by containing CO ₂Emission gases be blown into and contact with such solid particle aggregate, and wish that the emission gases that is blown into contacts with the solid particle that contains suitable moisture (more wishing the water attached to solid particles surface), makes CO especially ₂Become CaCO ₃, be fixed on the solid particle, can effectively absorb and remove CO ₂

The present invention is based on such understanding, and its feature is as follows.

[1] method of the carbon dioxide gas of minimizing discharging is characterized by: containing CO ₂Emission gases be blown into and contain CaO and/or Ca (OH) ₂The solid particle aggregate, it is contacted, CO in the emission gases with the solid particle aggregate ₂Become CaCO ₃Be fixed on the solid particle, thereby make CO in the emission gases ₂Concentration reduces.

[2] reduce the method for the carbon dioxide gas of discharging, it is characterized by: in the method for above-mentioned [1], and contain CO ₂The main solid particle of emission gases contact contain water.

[3] reduce the method for the carbon dioxide gas of discharging, it is characterized by: in the method for above-mentioned [2], and contain CO ₂The main solid particles surface of emission gases contact attached water is arranged.

[4] reduce the method for the carbon dioxide gas of discharging, it is characterized by: in the method for above-mentioned [2] or [3], and contain CO ₂The moisture content of solid particle aggregate of emission gases contact be 3～20%.

[5] method of the carbon dioxide gas of minimizing discharging, it is characterized by: in any method of above-mentioned [1]～[4], the granularity of solid particle is basically below 5mm.

[6] to reduce the method for the carbon dioxide gas of discharging, it is characterized by: in any method of above-mentioned [1]～[5], to make the CO that contains that is blown in order contacting in the space with the solid particle aggregate ₂The temperature of emission gases is lower than the water boiling point in this space.

[7] method of the carbon dioxide gas of minimizing discharging is characterized by: in appointing of above-mentioned [1]～[6]

In a kind of method, make to contain CO ₂Temperature remains on below the water boiling point in emission gases and the space that the solid particle aggregate contacts.

[8] reduce the method for the carbon dioxide gas of discharging, it is characterized by: in any method of above-mentioned [1]～[7], contain CO making ₂In emission gases and the space that the solid particle aggregate contacts, with contain CO ₂The temperature of the solid particle aggregate of emission gases contact remains on below the water boiling point.

[9] method of the carbon dioxide gas of minimizing discharging is characterized by: in any method of above-mentioned [1]～[8], pressurized emission gases is contacted with the solid particle aggregate.

[10] reduce the method for the carbon dioxide gas of discharging, it is characterized by: in any method of above-mentioned [1]～[9], contact with the solid particle aggregate after making the emission gases water saturation.

The CaO that contains in the solid particle, Ca (OH) in the present invention ₂At least be just passable, therefore also comprise CaO, Ca (OH) as mineral as the part of solid particle composition ₂Outside 2CaOSiO ₂, 3CaOSiO ₂, glass etc., be present in material in the solid particle as a part of forming.

The 2nd purpose of the present invention is: provide a kind of pH value that can not cause seawater and river to raise, and have favourable subaqueous stone material of sinking and its manufacture method of algal grown and fish, the breeding of Jie's class and utilize this stone material to build the method for algae field.

In order to achieve the above object, the invention provides the subaqueous stone material of sinking of the method manufacturing that utilizes following operation composition:

The mixture that the granular slag of preparing to produce in the steel manufacture process is formed; And

This mixture is carried out carbonating handle, generate carbonate, make the said mixture consolidated block as adhesive with the carbonate that generates.

Both can be used for the stone material of the marine usefulness of sinking with the stone material in the sinking water of the method manufacturing, also can be used for sinking at light subaqueous stone materials such as rivers.

Granular furnace charge both can be to select at least a furnace charge from a pile of being made up of powder shape slag, coarse grain shape slag, fritter shape slag, also can remove powder shape or the coarse-grained slag that iron block is handled with process.

The invention provides the manufacture method of the subaqueous stone material of forming by following operation of sinking:

The preparatory process of the mixture that the granular slag that is produced by steel manufacture process is formed;

Form the operation of packed layer with this mixture; And

Mixture effect with carbon dioxide and packed layer makes it that carbonation reaction take place, and makes the operation of this mixture consolidated block.

The operation that forms packed layer can be piled up formation with mixture.

The invention provides the algae field method of construction of forming by following operation:

In existing algae field, make the interim sinking of material of weight composition seaweeds the operation of giving birth to and growing on the surface of this material;

This material is taken out the operation of being transplanted to the place that to build the algae field as kind of material;

Configuration seaweeds to give birth to the material of required other, the operation that the seaweeds on this kind material is bred on other materials around this kind material.

Above-mentioned operation is to build an example of algae field method, does not adopt the method also passable.

Brief description of drawings

Fig. 1 is for inferring the CO in the emission gases ₂Be absorbed schematic diagram with fixed mechanism in solid particles surface.

Fig. 2 is the diagram of a form of implementation of the inventive method of explanation employing solid particle aggregate fluidized bed.

Fig. 3 is the diagram of a form of implementation of the inventive method of explanation employing rotary kiln.

Fig. 4 is for illustrating that the inventive method is containing CO ₂Emission gases be blown into the diagram of a form of implementation of solid particle aggregate packed layer by a direction.

Fig. 5 is the marine diagram with the stone material manufacture method of explanation sinking of the present invention.

Fig. 6 is the diagram of key diagram 5 manufacture method object lessons.

Fig. 7 is the marine diagram with the stone material manufacture method of explanation other sinkings of the present invention.

Fig. 8 is the diagram of key diagram 7 manufacture method object lessons.

Fig. 9 for explanation the present invention with the stone material of sinking korneforos make the structure of artificial fish pass, in the place mat in artificial riverbed, the diagram of structure under the sinking situation.

Figure 10 is the diagram of explanation sinking of the present invention korneforos with the stone material manufacture method.

Figure 11 is the diagram of explanation sinking of the present invention korneforos with stone material manufacture method object lesson.

The optimised form that carries out an invention

First form of implementation of the present invention is as follows: as CO ₂Absorbing material use slag and concrete etc. such contain CaO (and/or Ca (OH) ₂) the solid particle aggregate, make to contain CO ₂Emission gases solid particle aggregate contact therewith, by following reaction the CO in the emission gases ₂Become CaCO ₃, be fixed on the solid particle CO in absorption and the removal emission gases ₂As the method that this emission gases is contacted with the solid particle aggregate, wish to adopt the method that is blown into to the solid particle aggregate in this case, more wish it is to be blown into from a direction.Blowing method does not limit from the top in this case, the side, or the below is blown into, but the method that is blown into from the below is operated easily.

CaO (solid particle)+CO ₂(emission gases) → CaCO ₃(solid particle)

Just knew in the past, and utilized slag etc. to contain the solid particle aggregate of CaO, with CO ₂Carry out carbonation reaction and make its sclerosis, the technology that this hardenite uses as the civil construction material, the idea with former is opposite fully in the present invention, utilizes the solid particle aggregate and the CO that contain CaO ₂Carry out carbonation reaction, reduce the CO in the emission gases ₂, be to discharge CO in the gas as reducing ₂Method set up.

Utilization contains the solid particle aggregate of CaO, contains CO by making ₂Emission gases solid particle aggregate contact therewith, CO in the emission gases ₂Become CaCO ₃Be fixed on the solid particle, by an amount of moisture that is contained in the solid particle emission gases is contacted with solid particle, preferably under the state of solid particles surface attached water (moisture film), contact, can improve solid particle the CO in the emission gases with emission gases ₂Absorptivity.Therefore the main solid particle of this form formation solid particle aggregate contains moisture, more wishes at surface attachment water.

Contain moisture at solid particle, the CO in the emission gases is particularly arranged under the situation of surface attachment water ₂Reaction with solid particle, become molten Ca (Ca ion) and the reaction of molten carbon dioxide gas in surface attachment water from emission gases in (diffusion) surface attachment water from solid particle, got surface attachment water and CO clear by such solid particle ₂Reaction, to absorb and fixed discharge gas in CO ₂Effective especially.

That is to say,, think with the CO that makes in the emission gases according to inventor's imagination originally ₂Generate CaCO with the Ca reaction in the solid particle ₃Thereby, be fixed on the method on the solid particle, separate out CaCO with the carrying out of reaction in whole solid particles surface ₃, hinder the diffusion of the Ca ion in the solid particle, can not expect to have plant-scale, practical, high-caliber CO ₂Absorption efficiency.Opposite fully with such anticipation, have moisture at solid particle, particularly have under the state of surface attachment water, by with CO ₂Reaction can absorb CO with high efficient ₂

Its reason may not be clear, thinks following reason.

Fig. 1 is for inferring CO in the emission gases ₂The schematic diagram of the mechanism that is absorbed and fixes in solid particles surface.As shown in Figure 1, there are under the state of surface attachment water Ca ion, CO in the solid particles surface that contains CaO ₂(carbonic acid ion) dissolves near solid particle one side with near emission gases one side from surface attachment water respectively, and they react in surface attachment water, CaCO ₃Mainly separate out CaCO when separating out in solid particles surface ₃The core of separating out be not uniform generation in water, but be easy to generate inhomogeneous forming core, so CaCO in solid particles surface ₃Separate out and growing up subsequently occurs over just the specific region of solid particles surface.CaCO does not take place in what its utilization as a result had a significant proportion ₃The solid particles surface zone of separating out and growing up, can keep from this zone and to surface attachment water, supply with (stripping) Ca ion, so think and can absorb effectively and fixation of C O at short notice ₂

Best form of implementation with regard to this form describes below.

In this form as CO ₂What absorbing material used is that its component is for containing CaO, Ca (OH) ₂One of the solid particle aggregate.The Ca that contains in the solid particle (OH) ₂Also the same and CO with CaO ₂Reaction can become CaCO to it ₃And fix, so solid particle also can be to contain Ca (OH) ₂Material.As previously mentioned, the CaO that contains in the solid particle, Ca (OH) ₂Can be the part that solid particle is formed at least, therefore also comprise CaO, Ca (OH) as mineral ₂Outside 2CaOSiO ₂, 3CaOSiO ₂, glass etc., be present in the solid particle as a part of material that is this component.

As such solid particle, special hope is to contain CaO (and/or Ca (OH) ₂) slag that produces in high concrete and the steel manufacture process.Below this point, to describe in detail.

There is no particular limitation for the granularity of solid particle, but in order to guarantee the contact area with emission gases, react fully and carry out, wish fine size, specifically basically (that is to say to remove and unavoidably will contain beyond the big solid particle of granularity) below 5mm, preferably the granularity below 1mm.In fact wish that the following particle of 5mm is more than 90%.

As previously mentioned, adopt the method for this form, in order to ensure CO in solid particle and the emission gases ₂Reaction, wish that the main solid particle contact with emission gases contains suitable moisture, have again, wish that the best main solid particle that contacts with emission gases has surface attachment water.This so-called surface attachment water is meant that outside the moisture that particle-removing inside is contained, the solid particle outer surface also contains water in the moisture that coexists with solid particle.From same viewpoint, wish that solid particle aggregate moisture content is 3～20%.Therefore in order to ensure the moisture of solid particle and its aggregate like this, wish as required to add moisture at solid particles aggregate in advance.

Need be the CO that contains that contacts with the solid particle aggregate ₂The temperature of emission gases bring up to a certain degree, quicken reaction with solid particle, but the temperature of the emission gases that in the space that contacts with the solid particle aggregate (to call reaction compartment in the following text), imports, if surpass the boiling point of the water in this reaction compartment, attached water evaporation on the solid particle has hindered reaction on the contrary.Wish that for this reason temperature of exhaust gas will be below the boiling point of water in reaction compartment.Same reason wish to guarantee the interior temperature of reaction compartment below the boiling point of water, and then in reaction compartment, the temperature of solid particle aggregate will guarantee below the boiling point of water also.

From same viewpoint, wish that the water vapor concentration in the emission gases wants high, utilize to make emission gases it contain saturated II by the medium means of water in advance for this reason ₂O makes it contact with the solid particle aggregate then.

As absorbing CO ₂The solid particle aggregate of material is if contain CaO and/or Ca (OH) ₂The solid particle aggregate, then have no particular limits, particularly from CaO (and/or Ca (OH) ₂) content height and can to utilize this point, hope again from resource be slag and the concrete (for example Fei concrete) that produces in the steel manufacture process.Therefore wish that the solid particle that constitutes the solid particle aggregate has a part at least, wish that especially main solid particle is slag and/or concrete.

As absorbing CO ₂The solid particle aggregate of material except that above-mentioned slag, concrete, can also be mortar, glass, alumina cement, contain CaO refractory material, contain the refractory material of MgO etc., can use mixing more than a kind of these solid particle aggregates or use separately, perhaps mix use with slag and/or concrete.

The CaO/SiO of these solid particle aggregates ₂Weight ratio (basicity) height, with CO ₂Reaction well, from this viewpoint, CaO/SiO ₂Weight ratio to be preferably in more than 1.5 more than 1.2.

About 13～55% (the percentage by weight wt%) of CaO concentration of the slag that general steel manufacture process produces, about 5～the 15wt% of CaO concentration (the CaO concentration in the cement: 50～60wt%) of concrete (for example waste concrete), because these things are very easy to obtain, and we can say as CO ₂The solid particle used of absorbing material be very suitable.

The slag that steel manufacture process produces is adducible to be had: the blast furnace series slag of blast furnace slow cooling slag, blast furnace water quenching slag etc.; The copper smelter slag of the decarburization slag that operations such as preliminary treatment stove, converter, casting produce, dephosphorization slag, desulfurization slag, desiliconization slag, casting slag etc., ore reduction slag, electric-furnace slag etc., do not limit these slags, can mix yet and use two or more slags.

The slag that produces in the steel manufacture process contains a considerable amount of ferrous components (granular iron etc.), if the solid particle aggregate of these slags uses like this, only the composition because of iron will make the CaO concentration in the solid particle aggregate reduce, and therefore wishes to use the slag through iron block (composition of iron) recycling.Owing to generally carry out this iron block (composition of iron) recycling, be in order to use the composition that is contained in the iron in the slag in the steel manufacture process again, so will carry out break process to slag in order to reclaim iron block usually, utilize means such as magnetic separation to reclaim and remove a considerable amount of iron that contain in the slag.

As concrete, for example can utilize the waste concrete of demolition building and civil structure etc. etc.

These raw material are broken into powdery or granular as required, use as the solid particle aggregate.

As previously mentioned, as absorbing CO ₂The solid particle aggregate of material, from CO ₂The viewpoint of reactivity worth, CaO/SiO ₂Weight ratio, basicity just, height is good a bit.Water granulated slag CaO/SiO for example ₂The solid particle aggregate of weight ratio less than 1.5 because the solvability of Ca ion is low, with CO ₂Underaction, therefore not talkative having given full play to as CO ₂The function of absorbing material.This is because the low solid particle of basicity must carry out the calcium silicates (2CaOSiO for example of percarbonic acidization ₂, 3 CaOSiO ₂) and the many causes of CaO content is few or water granulated slag the is such nature of glass.

So low solid particle (general CaO/SiO of these basicity ₂Weight ratio less than 1.5) aggregate is as CO ₂When absorbing material used, the solid particle that basicity is high can be used as the alkaline accelerator that improves Ca ion solvability in this low basicity solid particle, the solid particle that hope can be high with basicity, preferably CaO/SiO ₂Weight ratio be that solid particle more than 1.8 mixes, (preferably further humid air maintenance (hydration maintenance) after) under the state that is added with water to it as CO ₂Absorbing material uses.Under the condition that moisture exists, CaO/SiO ₂Weight ratio is the high basicity solid particle more than 1.8, acts on low basicity solid particle as the alkaline accelerator that hangs down the basicity solid particle, can promote the hydration of low basicity solid particle.

For example under the situation of calcium silicates and the poor solid particle of CaO, with calcium silicates in the alkaline accelerator promotion solid particle and the hydration of CaO, its result becomes the state that the Ca ion is dissolved easily from solid particle, even calcium silicates is the same few originally together with CaO content, but improved the solvability of CaO generally.Under the situation of the many solid particles of the nature of glass, utilize alkaline accelerator to disconnect and form vitreous silicate network, also promote their hydration simultaneously, but its result can increase the CaO of carbonating.

Hydration is carried out in maintenance in humid air (hydration maintenance) after adding water, makes CaO become the state of easy carbonating, to improving CO ₂Absorptivity is effective.Also be; because the alkali dissolving needs the regular hour; so that the solid particle of the solid particle of low basicity and high basicity mix; only depend on that to add the effect of solvability of Ca ion that water improves the solid particle of low basicity be inadequate; therefore after two solid particle aggregates mixed, hope will be through the humid air maintenance of certain hour.

As the back will be narrated, can make solid particle occur chapping or playing the effect that makes the solid particle refinement by such humid air maintenance, also can improve CO from this respect ₂Absorbability.

The humid air maintenance, for example above-mentioned high basicity solid particle aggregate and low basicity solid particle aggregate mix, behind mixing under the situation of suitably moisture existence, can prevent that with sheet of vinyl covering etc. the straightforward procedure of moisture drying from carrying out to mixture, prevent solid particle carbonating in the maintenance, in fact wish do not containing CO ₂Atmosphere in, perhaps in maintenance, in fact replenish CO at least ₂Atmosphere in carry out, for example wish in cutting off the space (atmosphere) of atmosphere, to carry out.In the atmosphere of this space, be the CO that begins to contain in the atmosphere ₂, and no longer replenish more CO ₂

Not special regulation of the time of humid air maintenance, and the effect that will fully obtain the humid air maintenance was wanted more than 12 hours, preferably carried out more than 24 hours.

Also can be after carrying out this humid air maintenance, the mixture fragmentation, as CO ₂Absorbing material uses.Utilize such break process increase and contain CO ₂The contact area of emission gases, improve and CO ₂Reaction efficiency.

Below just effectively improve solid particle to CO ₂The method of absorbability describe.

As absorbing CO ₂The solid particle that utilizes of material (for example waste concrete and steel manufacture process produce slag) be generally block or granular since to make solid particle inside all with CO ₂Reaction needed is difficult to effectively utilize the inner CaO resource of solid particle to absorb CO so exist for a long time ₂Tendency.Solve such problem, it is effective utilizing the method for block or granular solid particle by humid air maintenance (hydration maintenance) to make its hydration expansion, be full of cracks occurs or split making grain refine by such hydration expansion solid particle, make CO thus because of be full of cracks ₂The solid particles surface area that can contact increases, so utilize the CaO resource to absorb CO ₂Efficient improve.In addition owing to making the material that contains CaO in the solid particle become the hydrate that carries out carbonation reaction easily, so, can improve and utilize the CaO resource to absorb CO from this respect by the humid air maintenance ₂Efficient.

When utilizing the humid air maintenance that the hydration of solid particle aggregate is expanded, be actually a solid particle aggregate and be placed on and do not contain CO ₂Atmosphere in, or be placed at least and in maintenance, no longer replenish CO ₂Atmosphere in, wish to carry out the humid air maintenance under the condition of moisture existing.The solid particle aggregate in the space that is placed into the humid air maintenance before and/or want the solid particles aggregate to supply water afterwards, the solid particles aggregate adds the method for cold water or warm water, can adopt the method for the solid particle aggregate winding-up steam in being placed on humid air maintenance space.

In fact do not containing CO ₂Atmosphere in, or in maintenance, no longer replenish CO at least ₂Atmosphere in carry out the humid air maintenance owing to make solid particle that carbonation reaction not take place as far as possible, wish for example in the space (atmosphere) that cuts off atmosphere, to carry out the humid air maintenance.The CO that the atmosphere in this space comes into existence and contains in the atmosphere ₂, and no longer replenish more CO ₂

When wanting the solid particles aggregate to add warm water, on the viewpoint of maintenance efficient, wish to add the warm water more than 60 ℃.

Solid particle aggregate through this humid air maintenance can be as CO ₂Absorbing material use.

Make the not special regulation of concrete means that emission gases contacts with the solid particle aggregate, from the easy degree of the loading and unloading of treatment effeciency and solid particle aggregate, suitable mode can be enumerated following several:

(1) make emission gases become mobile gas, the mode that emission gases is contacted with the solid particle aggregate;

(2) mode that emission gases and solid particle aggregate are contacted in rotary kiln;

(3) form the packed layer of filling the solid particle aggregate, by in this packed layer, feeding emission gases, the mode that emission gases is contacted with the solid particle aggregate.

Fig. 2 is the figure of the form of implementation of expression aforesaid way (1), and 1 is treatment trough, is provided with gas dispersion plate 100 in the bottom, and its top constitutes the space A that forms fluidized bed; The 2nd, hitherward manage the feedway that the solid particle aggregate is provided in the groove 1; The 3rd, supply contains CO in treatment trough 1 (bellows 110 of dispersion plate 100 belows) ₂The gas supply pipe road of emission gases; The 4th, from the gas outlet pipe road of treatment trough 1 discharge emission gases; The 5th, at any time can be from the solid particle discharge line of taking-up solid particle aggregate in the treatment trough 1.

Adopt this processing mode, in the A of the space of treatment trough 1, supply with solid particle aggregates such as slag and concrete from feedway 2, the emission gases of supplying with in bellows 110 from gas supply pipe road 3 is blown into space A from dispersion plate 100 on the other hand, forms the fluidized bed of solid particle aggregate.CO in this fluidized bed in solid particle and the emission gases ₂Reaction, CO ₂Become CaCO ₃Be fixed on the solid particle.From treatment trough 1, discharge through gas outlet pipe road 4 by this reacted emission gases, and the solid particle in the treatment trough 1 is also according to absorbing CO ₂Degree (CO ₂Absorbability) suitably discharge solid particles from pipeline 5.

Be provided with a plurality of treatment troughs of in Fig. 2, representing with double dot dash line, to these treatment troughs 1,1a, 1b ... be connected in series with the emission gases service, just the emission gases of discharging from treatment trough 1 is delivered to treatment trough 1a, deliver to treatment trough 1b from the emission gases that treatment trough 1a discharges, by treatment trough sequential processes, can make the CO in the emission gases effectively with a plurality of serial connections ₂Reduce.

The form of fluidized bed is arbitrarily during with (1) processing mode, is not limited to the form of implementation of Fig. 2.

Fig. 3 represents a form of implementation of aforesaid way (2), the 6th, rotary kiln; The 7th, the solid particle aggregate is supplied with feedway in this rotary kiln 6; The 8th, containing CO ₂Emission gases supply with gas supply pipe road in the rotary kiln; The 9th, from the gas outlet pipe road of rotary kiln 6 discharge emission gases; The 10th, the solid particle discharge portion of solid particle aggregate in the discharge rotary kiln.

Adopt this to handle the words of mode, in the processing usefulness space of rotary kiln 6, supply with solid particle aggregates such as slag and concrete from feedway 7,8 supply with emission gases from the gas supply pipe road, and the solid particle aggregate is while mixing and the CO in the emission gases rotary kiln 6 in ₂Reaction, CO ₂Become CaCO ₃Be fixed on the solid particle.This reacted emission gases is discharged from rotary kiln 6 by gas outlet pipe road 9, and the solid particle that arrives rotary kiln 6 outlets is also discharged from solid particle discharge portion 10.

In this mode, also be provided with a plurality of rotary kilns of in Fig. 3, representing with double dot dash line, to these rotary kilns 6,6a, 6b ... be connected in series with the emission gases service, just the emission gases of discharging from rotary kiln 6 is delivered to rotary kiln 6a, deliver to rotary kiln 6b from the emission gases that rotary kiln 6a discharges, by rotary kiln sequential processes, can make the CO in the emission gases effectively with a plurality of serial connections ₂Reduce.

The form of used rotary kiln is arbitrarily during with this processing mode (2), is not limited to the form of implementation of Fig. 3.

Fig. 4 represents a form of implementation of aforesaid way (3), the 11st, and the closed that formation solid particle aggregate packed layer is used or the container of semi-hermetic type; The 12nd, for winding-up in this container 11 contains CO ₂The gas supply pipe road of emission gases; The 13rd, from the gas outlet pipe road of container 11 discharge emission gases.

Adopt this to handle mode, the solid particle aggregate of packing in container 11 forms packed layer, supplies with emission gases from gas supply pipe road 12 to this packed layer, emission gases in the packed layer process of flowing through, the CO in the emission gases ₂With solid particle reaction, CO ₂Become CaCO ₃Be fixed on the solid particle.This reacted emission gases is discharged from container 11 by gas outlet pipe road 13.Because the solid particle aggregates in the container 11 are not to resemble the fluidized bed mobilely, because of carbonation reaction be bonded to bulk between the general circle particle with this mode.After the processing of carrying out certain hour, from container 11, take out the solid particle aggregate of bonding for this reason, in container 11, insert new solid particle aggregate then.

In this mode, also be provided with a plurality of containers of in Fig. 4, representing with double dot dash line, to these containers 11,11a, 11b ... be connected in series with the emission gases service, just the emission gases of discharging from container 11 is delivered to container 11a, deliver to container 11b from the emission gases that container 11a discharges, handle by containers sequentially, can make the CO in the emission gases effectively with a plurality of serial connections ₂Reduce.

The form of used container is arbitrarily during with this processing mode (3), is not limited to the form of implementation of Fig. 4.

Manage herein under the situation of mode (3), the little words of filling rate of the solid particle aggregate in the packed layer, the chance that emission gases contacts with solid particle is just few, influence treatment effeciency, so wishing the filling rate of solid particle aggregate is 40～90% percents volume to volume (following writing volume %), is preferably 50～75 volume %.

With the CO in the emission gases that the solid particle aggregate contacts ₂Concentration also can influence treatment effeciency, CO ₂The words treatment effeciency that concentration is low excessively reduces.In order to remove the CO in the emission gases effectively ₂, CO ₂Concentration is preferably in (best more than 10%) more than 5%.As what such emission gases can list CaCO arranged ₃The emission gases, coke oven emission gases, sintering furnace emission gases, bar plate heating stove emission gases, annealing furnace emission gases etc. of emission gases, hot-blast stove furnace gas, boiler of firing furnace.

On the characteristic of this formal approach, to CO ₂The lower emission gases of concentration ratio there is not obstacle as the processing object of this formal approach yet.

In order to improve treatment effeciency, wish to manage the state that subtend is handled the emission gases pressurization of supplying with in the space.Gas pressure is had no particular limits, because CO ₂The high more CO of dividing potential drop ₂Dissolution velocity in the solid particles surface attached water is big more, under pressurized state, contact with the solid particle aggregate, with under atmospheric pressure contact mutually specific energy effectively improve treatment effeciency.

The so-called CO that contains that handles object as this form ₂Emission gases, be exactly various device and device discharge contain CO ₂Gas, such emission gases (contains CO ₂Emission gases) source has no particular limits certainly.Whether also pay no attention to this emission gases is burning and exhausting, or not can be used as fuel waits and utilizes, for example steel manufacture process so-called bi-product gas (for example blast furnace furnace gas, converter gas, coke oven furnace gas etc.) that produce, that can be used as the fuel utilization also is included in the CO that contains that handles object as this form ₂Emission gases in.The CO that generally from the various emission gases that steel plant produce, contains high concentration ₂, as previously mentioned, all the final energy consumption of steel plant accounts for 11% of the Japan whole nation, so the processing of the various emission gases that the method for this form of we can say produces steel plant's (steel manufacture process) especially is very useful.

The bi-product gas heat that such steel manufacture process such as above-mentioned blast furnace furnace gas, converter gas, coke oven furnace gas produces is than higher, so usually as the gaseous fuel utilization.Contain many CO in these emission gases (bi-product gas) on the other hand ₂, and these CO ₂(act as a fuel and use the back) not only all is discharged in the atmosphere, and these contain CO ₂Part reduce caloric value as gaseous fuel, this just makes the consumption of gaseous fuel increase resultant CO ₂Amount further increases.

Therefore in the method for this form by from these bi-product gas, removing CO ₂, make gaseous fuel improve heat, follow the gaseous fuel consumption to reduce simultaneously, can reduce total CO ₂Growing amount.

On the basis of above-mentioned form of implementation, enumerate below than the better form of this form.

At first can enumerate following form about the solid particle that uses:

[a] reduces the method for the carbon dioxide gas of discharging, it is characterized in that: in any method of above-mentioned [1]～[10], it is the slag that concrete and/or steel manufacture process produce that the solid particle aggregate has a part at least.

[b] reduces the method for the carbon dioxide gas of discharging, it is characterized in that: in any method of above-mentioned [1]～[10], the main solid particle that constitutes the solid particle aggregate is the slag that concrete and/or steel manufacture process produce.

[c] reduces the method for the carbon dioxide gas of discharging, it is characterized in that: in the method for above-mentioned [a] or [b], slag is through reclaiming the slag that iron block is handled.

[d] reduces the method for the carbon dioxide gas of discharging, it is characterized in that: in any method of above-mentioned [1]～[10] and [a]～[c], and contain CO ₂The CaO/SiO of solid particle aggregate of emission gases contact ₂Weight ratio be more than 1.2.

[e] reduces the method for the carbon dioxide gas of discharging, and it is characterized in that: in any method of above-mentioned [1]～[10] and [a]～[d], emission gases makes in fluidized bed as flowing gas and contains CO ₂Emission gases contact with the solid particle aggregate.

[f] reduces the method for the carbon dioxide gas of discharging, it is characterized in that: in any method of above-mentioned [1]～[10] and [a]～[d], emission gases is contacted in rotary kiln with the solid particle aggregate.

[g] reduces the method for the carbon dioxide gas of discharging, it is characterized in that: in any method of above-mentioned [1]～[10] and [a]～[d], the solid particle aggregate forms the packed layer of filling, and by supply with emission gases in this packed layer, emission gases is contacted with the solid particle aggregate.

[h] reduces the method for the carbon dioxide gas of discharging, it is characterized in that: in the method for above-mentioned [g], by feed emission gases in this packed layer, emission gases is contacted with the solid particle aggregate.

[i] reduces the method for the carbon dioxide gas of discharging, it is characterized in that: in the method for above-mentioned [h], by emission gases is blown into from a direction, emission gases is contacted with the solid particle aggregate.

[j] reduces the method for the carbon dioxide gas of discharging, and it is characterized in that: in the method for above-mentioned [g], the filling rate of the solid particle aggregate in the packed layer is 40～90 volume %.

[k] reduces the method for the carbon dioxide gas of discharging, it is characterized in that: in any method of above-mentioned [1]～[10] and [a]～[j], with the CO in the emission gases that the solid particle aggregate contacts ₂Concentration is more than 5%.

[1] method of the carbon dioxide gas of minimizing discharging is characterized in that: in any method of above-mentioned [1]～[10] and [a]～[k], and CaO/SiO ₂The solid particle aggregate and the CaO/SiO of weight ratio less than 1.5 ₂Weight ratio be that solid particle aggregate more than 1.8 mixes, adding under the state of water and containing CO ₂Emission gases contact.

[m] reduces the method for the carbon dioxide gas of discharging, it is characterized in that: in the method for above-mentioned [1], and CaO/SiO ₂The solid particle aggregate of weight ratio less than 1.5 be the blast furnace water quenching slag.

[n] reduces the method for the carbon dioxide gas of discharging, it is characterized in that: in the method for above-mentioned [1] or [m], and CaO/SiO ₂The solid particle aggregate and the CaO/SiO of weight ratio less than 1.5 ₂Weight ratio be after solid particle aggregate more than 1.8 mixes, to carry out the humid air maintenance.

[o] reduces the method for the carbon dioxide gas of discharging, it is characterized in that: in the method for above-mentioned [n], carry out the hydration maintenance more than 12 hours.

[p] reduces the method for the carbon dioxide gas of discharging, it is characterized in that: in the method for above-mentioned [n] or [o], the solid particle aggregate is carried out break process after the humid air maintenance.

[q] reduces the method for the carbon dioxide gas of discharging, it is characterized in that: in any method of above-mentioned [1]～[10] and [a]～[p], the solid particle aggregate is carried out the humid air maintenance, make grain refine to scheme to expand to make solid particle be full of cracks occur and/or split because of be full of cracks by such hydration, make through the solid particle aggregate after this humid air maintenance with contain CO ₂Emission gases contact.

[r] reduces the method for the carbon dioxide gas of discharging, it is characterized in that: in the method for above-mentioned [q], in fact make do not containing CO ₂Atmosphere in, perhaps in maintenance, do not replenish CO at least ₂Atmosphere in carry out the humid air maintenance.

[s] reduces the method for the carbon dioxide gas of discharging, it is characterized in that: in the method for above-mentioned [q] or [f], add cold water or warm water for the solid particle aggregate that carries out the humid air maintenance.

[t] reduces the method for the carbon dioxide gas of discharging, it is characterized in that: in the method for above-mentioned [s], the temperature of the warm water that adds to the solid particle aggregate is more than 60 ℃.

[u] reduces the method for the carbon dioxide gas of discharging, it is characterized in that: in the method for above-mentioned [q] or [s], to the solid particle aggregate winding-up steam that carries out the humid air maintenance.

[v] reduces the method for the carbon dioxide gas of discharging, it is characterized in that: in any method of above-mentioned [1]～[10] and [a]～[u], contain CO ₂Emission gases be the emission gases that steel manufacture process produces.

[w] reduces the method for the carbon dioxide gas of discharging, it is characterized in that: in any method of above-mentioned [1]～[10] and [a]～[u], contain CO ₂Emission gases be to be used as the emission gases that fuel uses.

[x] reduces the method for the carbon dioxide gas of discharging, it is characterized in that: in the method for above-mentioned [w], the emission gases used of acting as a fuel is the bi-product gas (for example a kind or 2 kinds in blast furnace furnace gas, converter gas, the coke oven furnace gas) of steel manufacture process generation.

Narrate the embodiment of above-mentioned form below.

Embodiment 1

The long 2m of reactor, tubulose, there is the inlet and the outlet of emission gases at two ends, in reactor, fill slag (granularity: below the 10mm, CaO content: 35wt%, water content: 6%, filling rate: 50 volume %), 24 hours with gas pressure: average 0.3Kgf/cm ²In this slag packed layer, inject emission gases (CO ₂Concentration: 20%, temperature: 40 ℃), measured with slag and absorbed CO ₂The result, absorbed CO ₂With CO ₂The ratio of/slag is expressed as about 0.2.

With this CO ₂Uptake is the basis, calculates the CO in the reality ₂Uptake uses 200,000 tons/year slag can absorb the CO of 1.5 ten thousand tons/year (C conversions) ₂

Embodiment 2

The be prepared in advance dephosphorization slag of the CaO content 48wt% after the slow cooling is put into steelmaking container to this dephosphorization slag, is blown into steam under the state that cuts off with atmosphere, carries out 24 hours humid air maintenance (hydration maintenance).

Slag after this humid air maintenance and use the sieve screening of sieve aperture as 20mm respectively without the slag of maintenance becomes the granular slag that granularity is 20mm to the maximum.The sieve screening that is 5mm of these slag sieve apertures, studied the ratio that granularity is the granular slag of 5mm to the maximum.

Granularity be to the maximum 20mm, through the slag of above-mentioned humid air maintenance with without the slag of maintenance, be adjusted into and contain 6wt% moisture respectively, (fill 2kg among the φ 100mm * 200mm), the ratio from the sandbox bottom with 2L/min is blown into carbon dioxide gas (CO to sandbox respectively then ₂Concentration: 20%, temperature: 25 ℃) reclaim slag after 24 hours, measured absorption (fixing) CO ₂Amount.

It the results are shown in table 1.According to its result as can be seen, use through the embodiment 2-1 in the table 1 of humid air maintenance slag, because of the hydration of humid air maintenance is expanded, be full of cracks appears on slag granules, compare with the slag without maintenance, it is many that the ratio of the fine grained slag of the maximum 5mm of granularity has increased 10wt%, because hydration expanded slag particle cracks and refinement, compare without the embodiment 2-2 in the table 1 of the slag situation of maintenance with use, improved CO ₂Absorption efficiency, can absorb more CO ₂

Table 1

Treatment conditions	Embodiment 2-1	Embodiment 2-2
			The hydration curing time (hour)	24	0
The time of feeding carbon dioxide gas (hour)	24	24
			Be blown into the slag amount (wt%) of the preceding maximum 5mm of carbon dioxide gas	50	40
Absorb (fixing) CO 2Amount (wt%)	14	6

Be associated with the 1st form among the present invention, relate to the heavy stone material that is located at marine usefulness and manufacture method thereof, the heavy stone material used in the river and the manufacture method of manufacture method and algae field thereof of being located at as the 2nd form.Below these contents will be described in proper order.

The heavy stone material that is located at marine usefulness

Inventor test and research found that the following fact:

(1) CaCO that in carbonation reaction, generates ₃Or CaCO ₃And MgCO ₃As binding agent, make the slag of powder shape, coarse grain shape or little bulk, these slags that particularly contain an amount of iron part are fixed, by block is established marine stone material use as sinking, the pH value is raise, and can produce good effect cultivating aspect the seaweeds etc. yet.

(2) on the other hand, for must suppress the marine site that oxidation because of iron part causes the oxygen deprivation of seawater and excessive iron part is provided, the CaCO that in carbonation reaction, generates in seawater ₃Or CaCO ₃And MgCO ₃As binding agent, make through powder shape or the coarse-grained slag of removing the iron block processing fixed, by block is established marine stone material use as sinking, can not make the oxidation because of iron part cause the oxygen deprivation of seawater and in seawater, provide excessive iron part that the pH value is raise, and can produce good effect cultivating aspect the seaweeds etc. yet.

(3) in order to obtain the heavy stone material that is located at marine usefulness of above-mentioned bulk, from powder shape slag, at least select a kind of slag in coarse grain shape slag and the fritter shape slag, or through removing powder shape or the coarse-grained slag that iron block is handled, pile up or be filled to required density, by making this stockpile or packed layer under the situation that carbon dioxide gas exists, carbonation reaction take place, it is effective making the fixed method of above-mentioned slag, utilize this manufacture method, can make stone material, the also as easy as rolling off a log in addition stone material that manages bulk applicable to any density and the size of seabed and ocean current situation.

This form is based on above-mentioned understanding, and feature is as follows:

(1) this form is that the slag that produces with steel manufacture process is the heavy stone material that is located at marine usefulness of primary raw material, it is characterized by: the CaCO that generates in carbonation reaction ₃As binding agent, make above-mentioned slag be consolidated into bulk.This slag is at least a slag of electing in powder shape slag, coarse grain shape slag and the fritter shape slag.This slag also can be through removing powder shape or the coarse-grained slag that iron block is handled.

(2) this form is that the slag that produces with steel manufacture process is the heavy stone material that is located at marine usefulness of primary raw material, it is characterized by: the CaCO that generates in carbonation reaction ₃And MgCO ₃As binding agent, make above-mentioned slag be consolidated into bulk.But comprise MgCO ₃Situation as hydrate, hydroxide or double salt existence.This slag is at least a slag of electing in powder shape slag, coarse grain shape slag and the fritter shape slag.This slag also can be through removing powder shape or the coarse-grained slag that iron block is handled.

(3) this form is that the slag that produces with steel manufacture process and powder shape and/or coarse-grained interpolation material are the heavy stone material that is located at marine usefulness of primary raw material, it is characterized by: the CaCO that generates in carbonation reaction ₃As binding agent, make above-mentioned slag and add mixtures of material to be consolidated into bulk.This slag is at least a slag of electing from powder shape slag, coarse grain shape slag and fritter shape slag.This slag also can be through removing powder shape or the coarse-grained slag that iron block is handled.

(4) this form is that the slag that produces with steel manufacture process and powder shape and/or coarse-grained interpolation material are the heavy stone material that is located at marine usefulness of primary raw material, it is characterized by: the CaCO that generates in carbonation reaction ₃And MgCO ₃As binding agent, make above-mentioned slag and add mixtures of material to be consolidated into bulk.But comprise MgCO ₃Situation as hydrate, hydroxide or double salt existence.This slag is at least a slag of electing in powder shape slag, coarse grain shape slag and the fritter shape slag form a group.This slag also can be through removing powder shape or the coarse-grained slag that iron block is handled.

(5) being characterized as of the manufacture method of the heavy stone material that is located at marine usefulness: as required from CaO, Ca (OH) ₂, MgO, Mg (OH) ₂In select more than one, after the slag that produces in the steel manufacture process mixes, this slag is made escorial or is being formed packed layer in the space arbitrarily, under situation about existing at carbon dioxide gas, carbonation reaction takes place in escorial or packed layer, make slag fixed, obtain stone material behind the slag consolidated block.This slag is at least a slag of electing in powder shape slag, coarse grain shape slag and the fritter shape slag form a group.This slag also can be through removing powder shape or the coarse-grained slag that iron block is handled.

(6) being characterized as of the manufacture method of the heavy stone material that is located at marine usefulness: the powder shape (and/or) coarse-grained interpolation material and as required from CaO, Ca (OH) ₂, MgO, Mg (OH) ₂In select more than one, after the slag that produces in the steel manufacture process mixes, this slag is made escorial or is being formed packed layer in the space arbitrarily, under situation about existing at carbon dioxide gas, in escorial or packed layer carbonation reaction taking place, slag and packing material is solidified obtain block slag and the stone material that adds material.This slag is at least a slag of electing in powder shape slag, coarse grain shape slag and the fritter shape slag form a group.This slag also can be through removing powder shape or the coarse-grained slag that iron block is handled.

(7) in (1) to the form of [6], the slag that produces in the steel manufacture process also can be partly or entirely with obsolete material (for example Fei concrete) replacement that contains CaO.

This form is that the slag that produces with steel manufacture process is the heavy stone material that is located at marine usefulness of primary raw material, and the blast furnaces such as blast furnace slow cooling slag, blast furnace water quenching slag that have that can enumerate as such slag are that the steel-making of the decarburization slag that produces of operations such as slag, preliminary treatment, converter, casting, dephosphorization slag, desulfurization slag, desiliconization slag, casting slag etc. is slag, ore reduction slag, electric-furnace slag etc.Be not limited to these, also can mix slag more than 2 kinds and use.

Following Example is represented the composition of slag representative in these slags:

(1) decarburization slag ... T.Fe:17.5%, CaO:46.2%, SiO ₂: 11.7%, Al ₂O ₃: 1.4%, MgO:8.3%, MnO:6.2%, P:0.76%, S:0.04%

(2) dephosphorization slag ... T.Fe:5.8%, CaO:54.9%, SiO ₂: 18.4%, Al ₂O ₃: 2.8%, MgO:2.3%, MnO:1.9%, P:2.8%, S:0.03%

(3) desulfurization slag ... T.Fe:10.5%, CaO:50.3%, SiO ₂: 10.0%, Al ₂O ₃: 5.4%, MgO:1.1%, MnO:0.4%, P:0.13%, S:1.8%

(4) desiliconization slag ... T.Fe:10.5%, CaO:13.6%, SiO ₂: 43.7%, Al ₂O ₃: 3.8%, MgO:0.4%, MnO:15.8%, P:0.10%, S:0.19%

(5) blast furnace water quenching slag ... FeO:0.3%, CaO:42.0%, SiO ₂: 33.8%, MnO:0.3%, MgO:6.7%, Al ₂O ₃: 14.4%

In the slag that produces in the steel manufacture process, the P content height of dephosphorization slag, MnO content height in the desiliconization slag, therefore the raw material use as cement acquires a certain degree of difficulty, use these slags no problem in the present invention, can be used as the heavy primary raw material use that is located at marine with stone material.

The slag that produces in the above-mentioned steel manufacture process contains different many (general weight ratio is a few percent to 30%) iron block of the degree composition of iron (granular iron etc.), for the recycling in steel manufacture process of such iron, carry out the recovery of iron block in the slag.Be generally and reclaim iron block and will carry out break process to slag.Therefore the slag that contained efflorescence, mealization or little bulk state originally, inevitable through the slag that reclaims the iron block operation also is powder shape, coarse grain shape or little bulk.The particle diameter of the slag granules of this recovery iron block operation of general process is the cm order of magnitude or littler (for example 5cm is following).

The heavy stone material that is located at marine usefulness of this form be with at least a in such powder shape, coarse grain shape, the fritter shape slag be raw material.But the slag that uses in this form can be at least a in powder shape slag, coarse grain shape slag, the fritter shape slag, is not the condition of the above-mentioned recovery iron block operation of process as necessity.

It is to be an iron block recycling that is contained in the slag purpose that so-called recovery iron block is handled, and reclaims the processing of iron block from slag, and to handle such removal iron block in the slag be that the processing carried out of purpose is different with removing iron block.Therefore generally reclaim iron block handle in slag do not resemble and remove iron block and handle so finely brokenly, also remaining in the slag after processing have a considerable amount of iron blocks.In contrast, it is that slag is broken into powder shape or coarse grain shape that so-called removal iron block is handled, and except unavoidably remaining in the iron block in the slag, all remove the iron block in the slag.

When these slags were used for the raw material of the heavy stone material that is located at marine usefulness, that the iron-holder in the general slag is not less than was that the back will be narrated, also be fine as the situation of the raw material of stone material through removing slag that iron block handles.It would be better to say that it is good containing an amount of iron (the particularly metallic iron of granular iron etc. and the material of containing metal iron) in slag.This is because an amount of iron that contains in slag divides moltenly in seawater, replenishes the iron branch as nutritive salt in the seawater, and is favourable to the growth of seaweeds.The content of iron is being suitable more than 3% in weight ratio in slag for this reason.

Such iron branch can be with following two kinds of method adjustment in the slag:

(a) the partly or entirely remaining less than reclaiming of the iron block that contained originally in slag (granular iron etc.) gets off, and is utilized like this.

(b) iron block in slag in fact all (unavoidably except the iron block that can not remove) by remove iron block handle be removed after, as adding the material that material adds metallic iron or containing metal iron.

Under the situation of the method for employing (b), following benefit is arranged:

The part of the iron block that (1) contained originally in slag (granular iron etc.) does not reclaim, and in the method for remaining (a) that gets off, the amount of remaining iron block is difficult to correctly adjust in the slag.That is to say that the iron block that reclaims from slag is to utilize magnetic separation to wait to carry out, it is quite difficult that the recovery of carrying out iron block makes it to want remaining a certain amount of iron block.Even may, carrying out must carrying out miscellaneous control and operation in the magnetic separation.In contrast, in the method for (b), the iron block that contained originally in the slag all is removed basically, reclaims, owing to add the metallic iron of granular iron etc. or the material of containing metal iron again, being contained in the content that iron divides in the slag can control arbitrarily.

(2) for above-mentioned same reason, the iron branch (granular iron etc.) that contained originally in slag part does not reclaim, in the method for remaining (a) that gets off, remaining iron block shape and size etc. can not be selected in slag.Say as the back, general as can be made into the heavy preferably so-called granular iron of iron branch that contains in the marine slag that is located at stone material, utilize magnetic separation etc. from slag, to reclaim when removing the part iron block, not necessarily such granular iron is remaining to get off, we can say perhaps that granular iron is recovered and remove, have that the big iron block of shape is remaining to get off.In contrast, in the method for (b), shapes such as the metallic iron that adds in slag are selected arbitrarily with big I, and the resource of the iron of desired particulate iron is contained in the slag.

Therefore, obtain containing the slag of metallic iron and containing metal iron material, preferably the iron block in slag basically all (unavoidably except the iron block that can not remove) by remove iron block handle be removed after, be re-used as and add the material that material adds metallic iron or containing metal iron.

As what narrate later, removing generally that iron block handles is after the slag break process is become powder shape or coarse grain shape, utilizes method such as magnetic separation to carry out.Therefore comprise the slag that originally just exists with powder shape or coarse grain shape, and inevitable through the slag of removing the iron block processing with regard to the granular or coarse-grained slag of pulverize.Usually the slag granules particle diameter through such removal iron block operation is the mm order of magnitude or littler.

Except the iron block part of unavoidably not removing, wish to handle the iron block of removing as far as possible in the slag with above-mentioned removal iron block.Iron content (iron block) amount in the general slag of wishing to remove after iron block is handled is by weight being lower than 3%.For slag through the desirable iron-holder of the material of removing like this slag that iron block is handled, can access the metallic iron that contains granular iron and/or containing metal iron.

To consider following item for interpolation metallic iron and containing metal iron material in slag.The firstth, the material of metallic iron that shape is big or containing metal iron does not hinder the slag moulding.Another is the specific area that increases the metallic iron that contains in the slag, helps like this increasing from heavy being located at marine stone material and dissolving the iron that.From above-mentioned viewpoint, wish that particle is little and big or small neat, see that from this viewpoint granular iron is optimum.This granular iron not only can be the granular iron that reclaims from slag, any granular iron that also can use allotment in addition.

Because heavy causes such as marine site of establishing stone material, the iron block oxidation that contains in the slag causes when iron divides superfluous problem in seawater oxygen deprivation and the seawater, after the slag that uses removed iron block and handle, use, no longer add the material of above-mentioned metallic iron and containing metal iron etc. as the raw material of stone material.

The slag that above-mentioned steel manufacture process produces contains the different many iron blocks of degree, and the iron block in such slag also can be handled the iron block that reclaims significant proportion by above-mentioned recovery iron block.General slag composition and iron block are that the state that is interweaved mixes, so generally the break process of carrying out to a certain degree can not fully be removed iron block, after reclaiming the iron block operation, in slag, also a considerable amount of iron blocks can remainingly be arranged in reclaiming the iron block operation for this reason.Therefore the stone material of only using the slag through reclaiming iron block to obtain is heavy to be located at when marine, can produce the iron block oxidation that contains in the slag according to the difference in heavy marine site of establishing and cause that iron divides superfluous problem in seawater oxygen deprivation and the seawater.So, should use process removal iron block to handle the slag of removing main iron branch and make raw material for the stone material that is suitable for such marine site.

As mentioned above, general in slag slag and iron block be that the state that is interweaved mixes, so remove iron block with magnetic separation after must be when removing iron block and handle slag being managed powder shape or coarse grain shape.Therefore comprise powder shape or the coarse-grained slag that contained originally, and the granular or coarse grain shape of the inevitable pulverize of slag through removing the iron block operation.Generally the particle diameter through the slag granules of such removal iron block operation is the mm order of magnitude or littler (for example below the 5mm).

Therefore of the present inventionly heavyly establishing marine stone material be applicable to that the iron that has the seawater oxygen deprivation and supply with divides superfluous problem marine site in seawater, is being raw material through removing powder shape that iron block handles and/or coarse-grained slag.

Except inevitable remaining iron block composition, hope will be removed the iron block in the slag as far as possible in removing the iron block processing.Wish that generally iron branch (iron block) content in the slag is lower than percentage by weight 3%.

In this form, select at least a slag in the above-mentioned a pile of forming by powder shape slag, coarse grain shape slag, fritter shape slag, or through removing powder shape that iron block handles and/or coarse-grained slag as main material, the CaCO that in carbonation reaction, generates ₃Or CaCO ₃And MgCO ₃Make its fixed (carbonic acid curing) as binding agent, as can be seen Kuai Zhuan stone material as the algae field with stone material, to build the heavy stone materials that are located at marine usefulness such as stone material that seashore uses or fish shelter be well-adapted raw material.Above-mentioned at least a slag is included in removes the slag that iron block is handled the material of an amount of metallic iron of back adding and/or containing metal iron.

Utilize CaO and CO ₂Reaction, that is to say the CaCO that utilizes carbonation reaction to generate ₃Shot-like particle fixed itself be the technology of grasping very early, the shot-like particle that contains CaO is placed in the carbon dioxide atmosphere, presses the following formula reaction equation and generates CaCO ₃, this CaCO ₃Between particle, produce fixed phenomenon as binding agent.

CaO+CO ₂→CaCO ₃

Utilized the technology of such carbonation reaction in the past, for example delivered mixture with broken slag of steel-making wind and water as raw material, make autofrettage (for example spy open clear 57-92143 number, spy open clear 58-48642 number, spy and open clear 58-133334 number) of the pellet of the method (for example the spy opens clear 58-74559 number) of setting and hardening goods for building and non-sinter molding etc.But these technology in the past all are to be purpose with the pellet of making setting and hardening goods with desired intensity and non-sinter molding at short notice, and to the slag of powder shape, coarse grain shape or little bulk, perhaps utilize the fixed stone material that obtains of carbonation reaction through removing powder shape or the coarse-grained slag that iron block handles, its feature and vpg connection as heavy to be located at marine stone material be very suitable raw material without any explanation.

In addition the shot-like particle that contains MgO is placed in the carbon dioxide atmosphere and generates MgCO by carbonation reaction ₃, MgCO ₃Also can between particle, produce fixed phenomenon as binding agent.The MgCO that carbonation reaction by MgO generates ₃Water-free compound, hydrate (for example dihydrate, trihydrate, pentahydrate etc.), hydroxide various ways such as (basic magnesium carbonates), for example MgCO are arranged ₃Trihydrate generate by following formula reaction.

MgO+CO ₂+3H ₂O→MgCO ₃·3H ₂O

The slag that general steel manufacture process produces contains the CaO of a great deal of (being generally percentage by weight 20%～60%), of the present invention heavy to establish marine stone material be to select at least a slag from a pile of being made up of powder shape slag, coarse grain shape slag, fritter shape slag, perhaps with through CaO that contains in the powder shape of removing the iron block processing and/or the coarse-grained slag or the Ca (OH) that is obtained by the CaO variation ₂(comprise CaO, the Ca (OH) that add as required ₂), make it become CaCO by above-mentioned reaction ₃, CaCO ₃Make slag granules (containing under the situation of adding material) be consolidated into block stone material as binding agent for adding material granule and slag granules.

Contain a certain amount of MgO simultaneously with CaO in this external most slag, with heavy be located at marine use stone material, MgO or the Mg (OH) that by MgO variation obtain of such slag as this form of raw material ₂(comprise MgO, the Mg (OH) that add as required ₂), make it become MgCO by above-mentioned carbonation reaction ₃, MgCO ₃And CaCO ₃Make slag granules (containing under the situation of adding material) be consolidated into block stone material as binding agent for adding material granule and slag granules.

The MgCO that the carbonation reaction of above-mentioned MgO generates ₃Various ways such as water-free compound, hydrate, hydroxide are arranged, the MgCO that in the heavy stone material that is located at marine usefulness of the present invention, contains as binding agent ₃Can be any type of MgCO ₃The MgCO of conduct for example ₃Hydrate has MgCO ₃2H ₂O, MgCO ₃3H ₂O, MgCO ₃5H ₂O has MgCO as hydroxide (basic magnesium carbonate) ₃Mg (OH) ₂3H ₂O, 4MgCO ₃Mg (OH) ₂4H ₂O, 4MgCO ₃Mg (OH) ₂5H ₂O, 4MgCO ₃Mg (OH) ₂8H ₂O etc.MgCO is also arranged in addition ₃With the situation of other salt, also can be the MgCO that exists with such double salt form in conjunction with the double salt that forms ₃

CaO that contains in the slag that produces in steel manufacture process and part or all of MgO, absorption moisture or other reasons through certain hour are transformed into Ca (OH) sometimes ₂And Mg (OH) ₂Deng, above-mentioned this situation is no problem as the slag that utilizes in the present invention, these Ca (OH) ₂And Mg (OH) ₂Also can become CaCO respectively by carbonation reaction ₃And MgCO ₃, can access the heavy stone material that is located at marine usefulness of this form.

The stone material that this form heavy is located at marine usefulness as the algae field with stone material, the stone material of building usefulness such as stone material that seashore uses or fish shelter has following advantage:

1. (or the Ca (OH) that generates by CaO because the CaO that contains in the slag ₂) major part become CaCO ₃So, can prevent to raise because of CaO causes the pH value of seawater.Owing in slag, contain an amount of iron branch (the particularly material of metallic iron, containing metal iron), divide dissolving on the other hand, replenish in the seawater as the iron branch of nutritive salt by these iron, favourable to the growth of seaweeds.

2. from a pile of forming by powder shape slag, coarse grain shape slag, fritter shape slag, select at least a furnace charge, perhaps with powder shape and/or the coarse-grained slag handled through the removal iron block, solidify the block that obtains through carbonic acid, the character that totally has porous on (surface and inner), therefore marine alga is easily attached to stone surface, and, the composition (soluble silica and the iron for example talked about later grade) that can effectively promote seaweeds to grow that contains in the stone material is dissolved in the seawater easily because stone material inside also is cellular.Therefore block slag is remained untouched and compare as the fish shelter of the concrete system of aggregate when using and with slag, the effect of the growth of promotion seaweeds is arranged as sinking the stone material that is located at marine usefulness.

Particularly, must promote the growth of the seaweeds young on stone surface in order to promote the effect of marine alga reproduction and growth on the heavy stone material of establishing in the place of building the algae field.Marine the individuality of seaweeds is effective more the closer to stone material with dissolve active ingredient the stone material in water owing to be located at from this form heavy, thus effective especially to the growth of the young of seaweeds, so have the effect that can promote the seaweeds paedomorphosis.

When 3. block slag being used as the heavy stone material that is located at marine usefulness, be subjected to the restriction of the cooling means of molten slag and condition etc., generally its size has individual boundary (about general maximum 800mm), is difficult to obtain the neat bulk stone material of size.In contrast, at least a slag of selecting in a pile of forming by powder shape slag, coarse grain shape slag, fritter shape slag, or process is removed the powder shape of iron block processing and/or the stone material that coarse-grained slag is solidified into through the carbonic acid reaction, after solidifying, selection by the shape when carbonic acid solidifies or carbonic acid digs out the selection of shape etc., its big I is adjusted arbitrarily, also obtains the bulk stone material of algae field with special hope such as stone material and fish shelter easily.

4. heavy being located at marinely wishes to use according to situations such as seabed and ocean currents the stone material of optimal density (proportion) with stone material, and for example heavy when establishing the big stone material of density in the seabed that mud is piled up, stone material sinks in the mud, does not have the effect of algae field with stone material and fish shelter.At least a slag of selecting in a pile of forming by powder shape slag, coarse grain shape slag, fritter shape slag, or through removing powder shape and/or the coarse-grained slag that iron block is handled, be solidified into the stone material of powder shape and/or coarse-grained slag through the carbonic acid reaction, the bulk density (compacted density) of the slag when solidifying by suitable adjustment carbonic acid can be adjusted its density arbitrarily.

5. by through removal that powder shape that iron block handles and/or coarse-grained slag obtain heavy be located at marine when using stone material, owing to removed main iron block, the marine site that is used to exist the seawater oxygen deprivation and divides to the too much iron of seawater supply can not produce because of the iron block oxidation and causes seawater oxygen deprivation and the problem of dividing to the too much iron of seawater supply.Have again by what this slag of removing iron block obtained heavyly to be located at the marine stone material of using, the part of having removed iron block, it is more to help the composition that carbonic acid solidifies, so favourable to the intensity that guarantees stone material.

Since this form heavy be located at marine with stone material with the little slag of particle diameter, the CaCO that in carbonation reaction, generates ₃Or CaCO ₃And MgCO ₃Can be closely fixed as binding agent, therefore so enough intensity is arranged,, and also need not worry to produce in marine long-time placement and break and collapse even heavyly impacted when establishing in carrying with to marine.

Be located in the marine usefulness stone material at the heavy of this form, correspondence uses the situation in marine site to take the composition that suits respectively, at least a slag that can in a pile of forming by powder shape slag, coarse grain shape slag, fritter shape slag, select, or on the basis of the powder shape of process removal iron block processing and/or coarse-grained slag, can contain various interpolation materials (the interpolation material of powder shape, coarse grain shape or little bulk).For example these add the powder shape of the adducible powder shape that the soluble silica source arranged of materials or coarse grain shape material (soluble silica, contain the material of soluble silica), source of iron or coarse grain shape material (material of metallic iron, containing metal iron, iron oxide, contain the material of iron oxide), powder shape or coarse-grained CaO etc.Make as the CaO that adds material and add heavy being located in the stone material of marine usefulness to, must make the CaO that contains in the slag or have a mind to the CaO that adds to slag and want some have neither part nor lot in carbonation reaction at least in them, remaining down as CaO behind carbonation reaction.

Be located at the soluble silica that contains in the stone material of marine usefulness and source of iron (iron, iron oxide) to be dissolved in marine growth to seaweeds by them favourable heavy.From to the ability of marine dissolving with to being used for that seaweeds is grown, more wish it is the metallic iron in the source of iron and the material of containing metal iron.But the marine site that is used for there is the seawater oxygen deprivation and divides superfluous problem to the iron that seawater is supplied with, by through the heavy stone material that is located at marine usefulness of removing that powder shape that iron block handles and/or coarse-grained slag obtain the time, can not add the material of these metallic irons and containing metal iron.

Become the seabed form red tide reason phosphorus and form under the many situations of the sulfur content of reason of Kuroshio, contain a spot of CaO in the heavy stone material that is located at marine usefulness and can adsorb p and s, have the effect that prevents to produce red tide and Kuroshio.As previously mentioned, contain in stone material under the situation of a large amount of CaO, have the problem of the pH value rising that makes seawater, adsorb p and s, remaining a spot of CaO is just much of that behind carbonation reaction.

As the powder shape or the coarse grain shape material in soluble silica source, powder shape or coarse-grained soluble silica are arranged and/or contain the material of soluble silica.The material that contains soluble silica can use dust that coal combustion such as thermal power station produces and clinker ash etc.Wherein to contain percentage by weight be about 45～75% soluble silica to dust, and clinker ash contains the soluble silica of percentage by weight about 50～65%.

Because the blast furnace water quenching slag also contains many soluble silica, part or all of slag used blast-furnace slag, for example copper smelter slag and blast furnace water quenching slag mix to use, and the situation of adding as the interpolation material in soluble silica source also can obtain same effect.

Powder shape or coarse grain shape material as source of iron, material, powder shape or the coarse-grained iron oxide of such powder shape such as abrasive grit or coarse-grained metallic iron or containing metal iron arranged and/or contain the material etc. of iron oxide, especially easily adducible dust that the iron content that steel manufacture process produces arranged of the powder shape got of cheapness or coarse grain shape material and rolling iron scale etc.The dust of iron content is generally the dust of ironmaking, and such dust converts with Fe and contains iron oxide about 75%.Rolling iron scale converts with Fe and also contains iron oxide about 70%.

As previously mentioned, sink when establishing heavy stone material in the seabed that mud is piled up, stone material can sink in the mud, does not have the effect of algae field with stone material and fish shelter etc.So heavy stone material that is located at marine usefulness that uses in the marine site that this mud is piled up, wish to use the smaller slag of proportion as main raw material, specifically, using a part to compare the smaller water granulated slag of proportion with other slags at least, to make main raw material be effective.

The heavy stone material that is located at marine usefulness of this form has the proterties of porous, therefore obtains aforesaid effect.The porosity of stone material has no particular limits, and wishes that generally porosity is about 10～70%.

The heavy manufacture method that is located at the stone material of marine usefulness with regard to this form describes below.

Fig. 5 represents an example of manufacture method flow process of the present invention, and Fig. 6 represents the example by the manufacturing process of this manufacturing process.The slag that steel manufacture process produces at first reclaims iron block, removes the iron block of the significant proportion that contains in the slag.Generally reclaim in iron block operation at this and utilize disintegrating machine to make the slag granules diameter be broken into the cm order of magnitude or littler (for example below the 5cm), pulverize is granular, reclaim iron block behind coarse grain shape or the fritter shape slag.Slag is just passable for the particle diameter of degree that can reclaim iron block, even so slag is crushed to the thicker granularity of proterties of utilizing slag, also can reclaim iron block just, it is better to be crushed to the granularity that can remove iron block.

In above-mentioned recovery iron block, it is low more that iron block content can be removed the iron block processing more in the slag of recycling back, also can remaining an amount of iron block.This is because contain an amount of iron branch (the particularly material of metallic iron, containing metal iron) by being dissolved in the seawater in the slag, can replenish in the seawater as the iron branch of nutritive salt, and is favourable to the growth of seaweeds.So it is just passable more than 3% at percentage by weight that the general degree that reclaims reaches the content of the remaining iron block in recycling back.

Also have at slag and collapse into the situation of feeding under the state (that is to say that nature collapses into the state of powder shape, coarse grain shape or little bulk) of the particle diameter of recyclable iron block degree naturally, such slag also just be there is no need to carry out above-mentioned break process.The CaO that does not have scorification that for example contains in the slag is after the slag cooled and solidified, and the water reaction of being scattered during with airborne moisture or rainwater, cooling generates Ca (OH) ₂, can have the expand situation of collapse and efflorescence of slag during generation, basicity (CaO/SiO ₂) near generating 2 CaOSiO in 2 the slag ₂(C ₂S), C ₂S changes form and causes expansion in the slag cooling procedure, also have the situation of slag collapse, efflorescence, and just owing to these reasons, efflorescence, spheroidizing or little blocking can directly reclaim iron block to the slag of the particle diameter that can remove the iron block degree.

The general iron block that reclaims is handled and is adopted magnetic separator etc. to carry out magnetic separation (method of the granular iron in the slag being removed with magnet), is not limited to this, can use the different choosing method of proportion, for example utilizes the selection by winnowing etc. of the difference in specific gravity of iron block and slag.

Utilize the main iron block composition that reclaims in the recyclable slag of iron block method.

The slag of handling through above-mentioned recovery iron block is at least a slag of selecting from a pile that powder shape slag, coarse grain shape slag, fritter shape slag are formed, and delivers to next operation then and carries out carbonic acid curing, or deliver to its pretreatment process.But raw slag is so long as at least a slag of selecting in a pile of powder shape slag, coarse grain shape slag, fritter shape slag composition is just passable, therefore through the above-mentioned dispensable condition of recovery iron block operation.

The great majority that general process reclaims the slag of iron block operation have the difference on the big or small degree, powder shape or coarse-grained slag occupy certain ratio, even therefore be mixed with the bigger fritter shape slag granules of particle diameter in the slag, because powder shape or coarse-grained slag are filled out between little blocky-shaped particle, do not make slag granules carbonic acid solidify the intensity that reaches regulation so almost worry to hinder.But under the situation of the large percentage that situation that the slag only actually is made up of fritter shape slag granules and fritter shape slag account in slag,, can hinder to make slag granules carbonic acid solidify the intensity that reaches regulation because the contact area of slag granules diminishes.Therefore wish to carry out the granularity adjustment in this case, increase powder shape or coarse-grained slag ratio etc.

Iron in the slag divide the iron block (granular iron etc.) that in slag, contained originally do not resemble above-mentioned part or all of recovery, but remainingly get off, can utilize like this, and will launch to say as the front, to arbitrarily control the iron that contains in the slag and divide content, and shape and size that the iron that contains in the slag is divided choose at random, make the words that contain desired source of iron such as granular iron in the slag, in case handle iron block in the slag basically by after all (except the iron block that inevitably can not remove) removed through removing iron block, preferably adopt the method for adding as the material of metallic iron that adds material and/or containing metal iron.

Generally, removing that iron block handles is that with disintegrating machine slag to be crushed to particle diameter be to carry out behind the mm order of magnitude or littler (for example below the 5mm).But the diameter of slag granules reaches that to remove the degree that iron block handles just passable, thus about according to the proterties of slag etc. thicker granular just can remove iron block the time, can slag just be crushed to can remove iron block particle diameter just.About having granulated or coarse-grained slag, do not need to carry out above-mentioned break process sometimes by natural efflorescence etc. yet.When removing iron block and handle, except inevitable remaining iron block, wish to remove as far as possible the iron block in the slag, in the general slag of wishing to remove after iron block is handled, 3% of iron block content otherwise lumping weight amount percentage.

The general iron block of removing is handled and is adopted magnetic separator etc. to carry out magnetic separation (method of the granular iron in the slag being removed with magnet), is not limited to this, can use the choosing method of difference in specific gravity, for example utilizes the selection by winnowing etc. of the difference in specific gravity of iron block and slag.

In general, through removing the slag that iron block is handled, add the metallic iron of granular iron etc. and/or the material of containing metal iron for this in right amount, the material that can obtain containing metallic iron or containing metal iron has the slag that desirable iron divides content.The slag that obtains like this is powder shape and/or the coarse-grained slag that contains the material of metallic iron or containing metal iron, such slag is delivered to next carbonic acid curing process or deliver to its pretreatment process.Abrasive grit is best suited for adding in the slag as the material of metallic iron and containing metal iron.Such abrasive grit not only can be the abrasive grit that reclaims from slag, also can use any abrasive grit that can access in addition.

After Fig. 7 represents that slag is removed iron block and handled, do not add the material of metallic iron and containing metal iron, make a heavy example that is located at marine manufacturing process during with stone material, Fig. 8 represents an example by the manufacturing process of this manufacturing process.The slag that produces in the steel manufacture process is at first removed iron block and is handled, and removes main iron block composition.Because slag composition and iron block in the general slag are that the state that mutual densification interweaves mixes, remove iron block handle must be the slag pulverize granular or coarse grain shape, therefore generally with disintegrating machine slag being crushed to particle diameter is the mm order of magnitude or littler (for example 5mm is following), removes iron block after the fragmentation and handles.But the particle diameter of slag reaches that to remove the degree that iron block handles just passable, according to the proterties of slag etc. thicker granular just can remove iron block the time, can just be broken into the particle diameter that can remove iron block to slag.

Remove in the iron block processing at this, except inevitable remaining iron block, wish to remove as far as possible the iron block in the slag, general iron block content of wishing that the removal iron block is handled in the slag of back is lower than 3% of percentage by weight.

Under nature efflorescence or the spheroidizing state, particle diameter reaches the above-mentioned slag of can directly packing into that can remove the iron block degree, and such slag there is no need to carry out break process.The reason of this slag nature efflorescence because of these reason particle diameters reach the powdery that can remove the iron block degree or the slag of powder shape, can be removed iron block like this and handle as previously mentioned.

The general iron block of removing is handled and is adopted magnetic separator etc. to carry out magnetic separation (method of the granular iron in the slag being removed with magnet), is not limited to this, can use the choosing method of difference in specific gravity, for example utilizes the selection by winnowing etc. of the difference in specific gravity of iron block and slag.

Handle by above-mentioned removal iron block, removed iron block composition main in the slag.

The slag of handling through above-mentioned removal iron block is powder shape and/or coarse-grained slag, such slag is delivered to next carbonic acid curing process, or deliver to its pretreatment process.

At least a slag of selecting in the above-mentioned a pile of forming by powder shape slag, coarse grain shape slag, fritter shape slag, or through in the powder shape and/or coarse-grained slag of removing the iron block processing, add material as required, in carbonation reaction necessary CaO, MgO are arranged again in slag under the not enough situation, as required from CaO, MgO, Ca (OH) ₂, Mg (OH) ₂In select more than one to add, mix with slag.As adding material, for example can add the powder shape of the powder shape in soluble silica source or coarse grain shape material (soluble silica, contain the material of soluble silica), source of iron or coarse grain shape material (material of metallic iron, containing metal iron, iron oxide, contain the material of iron oxide), CaO etc., concrete example as previously mentioned.

Add in the material at these, soluble silica and source of iron (metallic iron, iron oxide) are by being dissolved in the growth that helps seaweeds in the seawater, from to the ability of marine dissolving with to being used for that seaweeds is grown, more wish it is the metallic iron in the source of iron and the material of containing metal iron.But the marine site that is used for there is the seawater oxygen deprivation and divides superfluous problem to the iron that seawater is supplied with, by through the heavy stone material that is located at marine usefulness of removing that powder shape that iron block handles and/or coarse-grained slag obtain the time, can not add the material of these metallic irons and containing metal iron.

Add the interpolation raw material of material and CaO etc. and the mixed method of slag in addition, can adopt following any method.For example from reclaiming the iron block treatment facility or removing the slag of discharging the iron block treatment facility and add the method that raw material mixes in hopper; In reclaiming iron block treatment facility or removal iron block treatment facility, join the method for mixing in the slag of removing after iron block is handled adding raw material; Method with the mixing of heavy-duty machineries such as excavator; The method of mixing with concrete mixer truck (concrete central mix plant) etc.

Also can carry out the moisture adjustment of slag as required in this stage.Adjusting problem about moisture will be described in detail in the back.

Solidify in order to carry out carbonic acid, as required through adding add material, mixing and carry out moisture adjustment etc. like this escorial of processing mound or be filled into space arbitrarily.

When escorial is mounded, also have no relations, but wish to make the carbon dioxide gas that is blown into can be fully mobile in whole stacking with the mode of stacking, and for preventing that slag from because of dispersing and rainwater causes loss, cover stacking with thin plate.

To slag be piled up or fill, for example can use with dividing plate surround three faces the hole, surround the sandbox of four faces or container etc. with dividing plate.Wherein pile up in the hole or fill the situation of slag also the situation with above-mentioned stacking is identical, hope covers stacking or packed layer with thin plate etc.Also wish to cover the slag packed layer or case lid is set in the situation of using sandbox or container with thin plate.Fig. 6 and Fig. 8 are illustrated in the situation that forms packed layer A in the sandbox.

The accumulating amount of slag or loading do not have specific restriction, for example several tons to the accumulating amount of hundreds of tons of scales or loading can, it is also passable to the accumulating amount or the loading of tens of blocks of stone materials perhaps to be equivalent to a stone material, can be quantity arbitrarily.But the accumulating amount of slag or loading are that stacking or the packed layer after the carbonic acid curing can be easily broken with heavy-duty machinery at most, be easy to block stone material is cut a hole to get off to transport, and the advantage that the block stone material that gets off has the concavo-convex section that adheres to that helps seaweeds is cut a hole in such fragmentation.Therefore from the function aspects of production capacity and algae field usefulness stone material and fish shelter, wish slag accumulating amount or loading will arrive to a certain degree more.

Corresponding to the density of the stone material that will make, hope will be adjusted the stacking of slag or the bulk density of packed layer (compacted density).That is to say that the heavy stone material that is located at marine usefulness wishes to adjust density according to the state in seabed etc., for example the seabed is under the situation of shale or mud matter, for stone material is sunk in mud and the mud, wish to use the lower stone material of density, the seabed is under the situations such as cay on the other hand, for stone material is flowed in ocean current, wish to use density than higher stone material.Because the gas porosity (porosity) of stone material causes the degree of adhering to, growing of seaweeds also different with the situation of dissolving the active ingredient that from stone material inside, also wish to use according to the difference adjustment in marine site the situation of the gas porosity of stone material sometimes in addition.

The density of the stone material made from the method for this form is relevant with the stacking of slag or the bulk density of packed layer (compacted density), therefore the degree of the compacting of slag stacking or packed layer to be adjusted according to above-mentioned needs, the density of stone material can be adjusted at an easy rate by adjusting bulk density.

The degree of slag stacking or packed layer compacting is arbitrarily, but common bulk proportion/true specific gravity that is to say that in 0.3～0.9 scope the porosity that will tamp in stacking or the packed layer is 70～10% degree.

The stacking of slag or the compacting of packed layer, can adopt the method for tamping with heavy-duty machinery from the top of stacking or packed layer, and the method that makes stacking or packed layer vibration compacting, when tamping, the bulk density of stacking or packed layer is adjusted by the degree of adjusting compacting.When making the low especially stone material of density, can not tamp yet, slag is piled up or fill after just carry out carbonic acid and solidify.

Concrete grammar as compacting, when for example the stacking in aforesaid hole, sandbox or container or packed layer being tamped, in advance the inboard of hole, sandbox or container make the expression target volume the sign line, the slag of knowing weight put into their inside after, tamp make stacking or packed layer above reach the height of above-mentioned sign line.

After the adjustment of finishing above stacking or the bulk proportion of packed layer, make its stacking or packed layer under the condition that carbon dioxide gas exists, carry out carbonation reaction, slag carbonic acid is solidified.Specifically in the stacking of slag or packed layer, be blown into carbon dioxide gas or contain the gas of carbon dioxide gas, or stacking or packed layer be placed on carbon dioxide gas or contain under the atmosphere of gas of carbon dioxide gas, slag is carried out carbonic acid solidify.

The method that is blown into carbon dioxide gas or contains the gas of carbon dioxide gas in stacking or packed layer has no particular limits, and in the bottom of stacking or packed layer device for blowing is set, and it is the most effective being blown into gas by such device for blowing gas.Specifically, in the bottom of stacking or packed layer (being their base plate under situation) with hole, sandbox or container, with suitable configuration density pipe arrangement that air feed uses or flexible pipe etc. are set, (for example 30～300mm * 40～400mm) are provided with the gas injection hole, can blow out carbon dioxide gas or contain the gas of carbon dioxide gas from the gas injection hole with suitable spacing on these pipe arrangements or flexible pipe.

In addition as stacking or packed layer being placed on carbon dioxide gas or containing method in the atmosphere of gas of carbon dioxide, can adopt stacking or packed layer are placed in the airtight space (comprising container etc.), in this space, supply with carbon dioxide gas or contain the gas of carbon dioxide with state arbitrarily.

As the carbonated gas that uses, for example the gas of Shi Heing has: emission gases (the general CO in sodalime factory of comprehensive steel plant ₂: about 25%) and heating furnace emission gases (general CO ₂: about 6.5%), but also be not limited only to these gases.Have again dense carbon dioxide can occur in the carbonated gas and spend problem low and that treatment effeciency reduces, do not have what special problem in addition.Therefore gas concentration lwevel has no particular limits, but considers to handle effectively, wishes that gas concentration lwevel is more than 3%.

The amount of being blown into of carbon dioxide gas or carbonated gas also has no particular limits in addition, and the immobilising degree of slag stacking or packed layer can be blown into gas just, generally can guarantee to be blown into the amount of gas at 0.004～0.5m as standard ³/ mint just can.The time (carbonating processing time) that is blown into gas also has no particular limits, and wishes it is carbon dioxide gas (CO as standard ₂) the amount of being blown into reach time more than 3% of slag weight, that is to say the amount that is converted into gas, every 1t material will be supplied with 15m ³Above carbon dioxide gas (CO ₂).

To the slag stacking or packed layer is blown into carbon dioxide gas or carbonated gas can be normal temperature, to compare with normal temperature, high-temperature gas is favourable from the ability aspect of reaction only.The upper limit of gas temperature is CaCO ₃Resolve into CaO and CO ₂, MgCO ₃Resolve into MgO and CO ₂Temperature, the temperature of using gases must be promptly to use high-temperature gas that the temperature of such decomposition does not take place yet.Other conditions such as state that the optimum temperature of practical operation also needs to consider moisture decide.

Utilizing the reaction of CaO, MgO and carbon dioxide gas that slag carbonic acid is solidified must have different optimum moisture differences such as moisture, the granularity of slag, and before carbonating was handled beginning, water content was suitable in 3～10% degree in the slag.This is owing to be dissolved in the water by CaO, MgO and carbon dioxide gas, promotes the result of carbonation reaction.Therefore after as required the moisture of slag being adjusted to only value, under the condition that carbon dioxide gas exists carbonation reaction takes place.Under the low excessively situation of slag water content, wish in the mixed process of Fig. 5, Fig. 7, in slag, to add water, the adjustment that improves the slag water content for this reason.In case carbon dioxide gas or carbonated gas is blown into makes H in the water ₂After O is saturated,, can prevent the drying of slag, promote carbonation reaction by blowing to stacking or packed layer.The value of the water content of the compressive strength maximum of the block after also can adjusting to the moisture of mixture carbonating and handle.The value of this water content is obtained by the following method:

(a), prepare to have added the raw slag of water of any amount more than 3 times of the water absorption rate of raw slag particle for the raw slag of 100 parts of weight.Above-mentioned water absorption rate is the fine aggregate stipulated among JIS A1109 or the A111O or the water absorption rate of coarse aggregate.

(b) various raw slag are filled in make packed layer in the sandbox, the porosity in the time of making drying is certain.

(c) be blown into a certain amount of 10～40 ℃ humidification carbon dioxide gas to packed layer, carry out the carbonating maintenance of certain hour, raw slag is solidified.

(d) measure the compressive strength of the slag after solidifying, obtained the maximum of compressive strength.The value of corresponding peaked moisture is only moisture.

By in slag stacking or packed layer, supplying with carbon dioxide gas or carbonated gas, as discussed previously, by CaO (or Ca (OH) ₂), MgO (or Mg (OH) ₂) generate CaCO with the reaction of carbon dioxide gas ₃, MgCO ₃, this CaCO ₃Or CaCO ₃And MgCO ₃Become binding agent make slag granules (with add the situation that material mixes under be the particle of slag granules and interpolation material) fixed.

After such carbonic acid curing is finished, with heavy-duty machinery stacking or packed layer are broken into suitable size as required, cut a hole the block heavy stone material that is located at marine usefulness.Therefore according to the size of cutter piece, can obtain the stone material of size arbitrarily.Usually the size that block stone material is cut a hole into 80～1500mm, fragmentation when breaking by cutting a hole forms the concavo-convex section that seaweeds adheres to easily on the stone material.

If enough little of the volume of packed layer in the manufacture method of this form, it is disconnected also passable as the stone material utilization like this not carry out above-mentioned cutter.

The manufacture method of this form has following advantage:

1. owing to be that slag carbonic acid is solidified, adjust bulk proportion, heavyly be located at marine density and can adjust simply with stone material by the compacting degree of adjusting stacking or packed layer.As previously mentioned, the heavy stone material that is located at marine usefulness is wished will be according to the situation of seabed and ocean current etc., suitably adjusts density and gas porosity, can be arbitrarily and carry out such adjustment simply, and be a big advantage as the heavy manufacture method that is located at the stone material of marine usefulness.Known the technology of making pelletizing with carbonic acid curing as former technology, the density of adjusting non-processing material in wide scope with such method of making particle is difficult.

2. the method for this form is that slag carbonic acid is solidified, carbonic acid solidifies the back stacking or packed layer is broken into suitable size, cut a hole into the block stone material of desirable size, or packed layer remained untouched use as block stone material, so the size of the stone material cut a hole and the size of packed layer are carried out suitable selection, (for example 80～1500mm) stone material also obtains the stone material of algae field with special bulk of wishing such as stone material and fish shelter easily to access any size.With the above-mentioned former technology of making pelletizing particle etc., the size of the block that obtains is at most about limit 30～50mm, and produces the little block of size inevitably.Therefore the method with this form can access the boulder material, has tangible advantage as the heavy manufacture method that is located at the stone material of marine usefulness.

3. carbonic acid solidifies the stacking or the packed layer heavy-duty machinery fragmentation of back slag, can access the block stone material of the convex-concave surface (section) that has seaweeds and adhere to easily by the method that adopts cutter to get block stone material.

The stone material that this form heavy is located at marine usefulness with the algae field with stone material, to build seashore be to have excellent characteristic under the purpose situation about using with stone material, fish shelter etc., except that such purpose, for example the seabed support is a purpose stone material etc. with stone material, with the bed mud that improves or purify the seabed, much less can be used for various purposes, even the occasion in that this purpose is used also can have above-mentioned good effect at the aspects such as growth of seaweeds.

Embodiment 3

Converter slag powder (the slag that contains fritter shape slag behind the recovery iron block, the iron content component: weight 12%) the about 30mm of maximum particle size of slag granules, and the following proportion of particles of granularity 5mm accounts for 70% of weight greatly, in the hole of wide 4m * depth 6m, the converter slag powder is piled into the 1.5m height, suitably the compacting back is the hole sealing, by air demand 50Nm ³The ratio of/hr supplies carbon dioxide gas three days, and slag carbonic acid is solidified.The slag that such carbonic acid solidifies is cut apart with the heavy-duty machinery fragmentation, obtained the stone material of algae field usefulness that size is approximately the bulk of 1.0～1.5m.

As a comparison case, flow into mortar in the sandbox that is of a size of 1.5m * 1.5m * 1.5m, the concrete block after the sclerosis is cut into 2 with disintegrating machine (rock cutting machine), obtains the stone material of the algae field usefulness of the plane of disruption.

Near the seabed of the 4m depth of water the selected natural algae field is as the place of making test algae field, 20 heavy respectively being located in the scope of the about 10m of diameter of the stone material of 15 of stone materials of above-mentioned present embodiment and Comparative Examples.The stone material of Comparative Examples is put the plane of disruption above the work.Heavy establish this stone material period selected natural algae field seaweeds to emit period before the spore, purpose is that marine precipitum does not cover the surface of stone material before the spore of seaweeds etc. adheres to.

The heavy result who establishes the place of 1 year this stone material of " Invest, Then Investigate " has confirmed to have on all stone materials seaweeds to adhere to and has grown, has investigated the growth amount of seaweeds, the consequently weight in wet base on the stone material of Comparative Examples: 956g/m with the crop investigation methods of gathering in a level ground ², the weight in wet base on the stone material of example of the present invention: 1121g/m ², confirmed that the adhesive rate and the developmental potency of seaweeds on the stone material of example of the present invention is good.

Embodiment 4

Converter slag powder below the granularity 3mm (through removing the pulverized slag that iron block is handled, the iron content component: weight 2%) is piled into the 1.5m height to the converter slag powder the hole of wide 4m * depth 6m in, suitably the compacting back seals the hole, presses air demand 50Nm ³The ratio of/hr supplies carbon dioxide gas three days, and slag carbonic acid is solidified.The slag that such carbonic acid solidifies is cut apart with the heavy-duty machinery fragmentation, obtained the stone material of algae field usefulness that size is approximately the bulk of 1.0～1.5m.

As a comparison case, flow into mortar in the sandbox that is of a size of 1.5m * 1.5m * 1.5m, the concrete block after the sclerosis is cut into 2 with disintegrating machine (rock cutting machine), obtains the stone material of the algae field usefulness of the plane of disruption.

Near the seabed of the 4m depth of water the selected natural algae field is as the place of making test algae field, 20 heavy respectively being located in the scope of the about 10m of diameter of the stone material of 15 of stone materials of the invention described above example and Comparative Examples.The stone material of Comparative Examples is put the plane of disruption above the work.The heavy seaweeds that is selected in natural algae field period of establishing this stone material will be emitted the period before the spore, and purpose is that marine precipitum does not cover the surface of stone material before the spore of seaweeds etc. adheres to.

The heavy result who establishes the place of 1 year this stone material of " Invest, Then Investigate " has confirmed to have on all stone materials seaweeds to adhere to and has grown, has investigated the growth amount of seaweeds, the consequently weight in wet base on the stone material of Comparative Examples: 579g/m with the crop investigation methods of gathering in a level ground ², the weight in wet base on the stone material of this form example: 695g/m ², confirmed that the adhesive rate and the developmental potency of seaweeds on the stone material of this form example is good.

As mentioned above, this form of employing does not cause seawater pH value to raise and oxygen deprivation, and as the stone material of algae field usefulness, when building stone material that seashore uses or fish shelter etc. and using, development at seaweeds also can be brought into play good performance, and the heavy stone material that is located at marine usefulness that can provide size and density to adjust easily is provided.

Adopt process of the present invention to remove the heavy stone material that is located at marine usefulness of the raw slag manufacturing of iron block processing, except above-mentioned effect is arranged, can also suppress the marine site that cause the seawater oxygen deprivation and in seawater, provide superfluous iron to divide because of oxidation that iron divides at needs, have the effect that causes the seawater oxygen deprivation and provide superfluous iron to divide in seawater because of oxidation that iron divides can be provided.

Particularly use the manufacture method of this form, owing to be under the state of stacking or packed layer, to make slag carry out carbonic acid to solidify, so the size of the stone material of utilize to adjust the degree of stacking or packed layer compacting, suitably chiseling after selecting carbonic acid to solidify and the size of packed layer etc. can be simply and make the heavy stone material that is located at marine usefulness of any density and size at low cost.

The expansion that has the phase change expansion of the γ-attitude calcium-silicate that generates in when cooling and produce because of the hydration of free CaO in slag etc. causes the character of efflorescence, the slag of such efflorescence was except the raw material use of a part as cement in the past, do not have other purposes, major part is destroyed.Atomized slag such in this form also can utilize as raw material, had any problem as the raw material utilization of cement etc. by the restriction of composition, also can utilize the slag (for example dephosphorization slag and desiliconization slag) that is difficult to effectively utilize as raw material, so from effectively utilizing the aspect of the slag that steel manufacture process produces, this also is very useful invention.

Heavy stone material and the manufacture method of using in the river thereof of establishing

Inventor test and research found that the following fact:

(1) slag of powder shape, coarse grain shape or little bulk, the slag that particularly contains an amount of iron branch generates CaCO through carbonation reaction ₃Or CaCO ₃And MgCO ₃, CaCO ₃Or CaCO ₃And MgCO ₃Make slag be consolidated into bulk as binding agent.Make the heavy stone material of using in the river of establishing with its pH value in river is raise, and the stone material of using as the riverbed in the river is heavy is located in the water or after the laying, have good effect in the development of the water plants of the formation of the living spaces of fish and algae etc.Particularly to heavy if after being laid on the manual construction position of fish pass etc. of the dykes and dams in river and embankment etc. and the artificial riverbed, as can be seen to the organism in water beyond the fish move and the development of water plant has good effect.

(2) on the other hand,, use, carbonation reaction takes place generate CaCO through removing powder shape or the coarse-grained slag that iron block is handled for suppressing because of the basin that iron divides oxidation to cause the oxygen deprivation of river and the iron of excess supply divides in river ₃Or CaCO ₃And MgCO ₃, use CaCO ₃Or CaCO ₃And MgCO ₃Make slag be consolidated into bulk as binding agent.With its do heavy establish the stone material of using in the river can not cause because of iron divide the oxygen deprivation of the river water that oxidation causes and in river water the iron branch of excess supply, and the pH value rising that can not make river, and the development of algae etc. had good effect.

(3) heavyly establish the stone material that the river is used for what can obtain above-mentioned bulk, the slag of powder shape, coarse grain shape or little bulk, or powder shape or coarse-grained slag that process removal iron block is handled are piled up or filling by desired density, by making this stacking or packed layer under the condition that carbon dioxide gas exists, carbonation reaction take place, be the fixed manufacture method of above-mentioned slag effective.Adopt such manufacture method can make at an easy rate applicable to situation such as riverbed and current and except that the riverbed is used etc. with, fish pass any density of other purposes and the stone material of size, also be very easy to the stone material of manufacturing bulk.

The feature of this form is as follows:

(1) this is to be the heavy stone material of using in the river of establishing of primary raw material with the slag that produces in the steel manufacture process, it is characterized by: the CaCO that generates in carbonation reaction ₃Make slag be consolidated into block stone material as binding agent.This slag is at least a slag of electing a group that forms from powder shape slag, coarse grain shape slag and fritter shape slag.This slag also can be through removing powder shape or the coarse-grained slag that iron block is handled.

(2) this is to be the heavy stone material of using in the river of establishing of primary raw material with the slag that produces in the steel manufacture process, it is characterized by: the CaCO that generates in carbonation reaction ₃And MgCO ₃Make slag be consolidated into block stone material as binding agent.But comprise MgCO ₃Situation about existing with hydrate, hydroxide or double salt form.This slag is at least a slag of electing a group that forms from powder shape slag, coarse grain shape slag and fritter shape slag.This slag also can be through removing powder shape or the coarse-grained slag that iron block is handled.

(3) this is to be the heavy stone material of using in the river of establishing of primary raw material with the slag that produces in the steel manufacture process and powder shape and/or coarse-grained interpolation material, it is characterized by: the CaCO that generates in carbonation reaction ₃Make slag and add the stone material that mixtures of material is consolidated into bulk as binding agent.This slag is at least a slag of electing from the combination that powder shape slag, coarse grain shape slag and fritter shape slag are formed.This slag also can be through removing powder shape or the coarse-grained slag that iron block is handled.

(4) this is to be the heavy stone material of using in the river of establishing of primary raw material with the slag that produces in the steel manufacture process and powder shape and/or coarse-grained interpolation material, it is characterized by: the CaCO that generates in carbonation reaction ₃And MgCO ₃Make slag and add the stone material that mixtures of material is consolidated into bulk as binding agent.But comprise MgCO ₃Situation about existing with hydrate, hydroxide or double salt form.This slag is at least a slag of electing from the combination that powder shape slag, coarse grain shape slag and fritter shape slag are formed.This slag also can be through removing powder shape or the coarse-grained slag that iron block is handled.

(5) this is to make heavy manufacture method of establishing the stone material of using in the river, it is characterized by: in the slag that produces in steel manufacture process, as required from CaO, Ca (OH) ₂, MgO, Mg (OH) ₂In select more than one and it mix after, with this slag stacking or arbitrarily making packed layer in the space, make this slag stacking or packed layer under the condition that carbon dioxide gas exists, carbonation reaction take place, make slag be consolidated into block stone material.This slag is at least a slag of electing from the combination that powder shape slag, coarse grain shape slag and fritter shape slag are formed.This slag also can be through removing powder shape or the coarse-grained slag that iron block is handled.

(6) this is to make heavy manufacture method of establishing the stone material of using in the river, it is characterized by: slag that produces in the steel manufacture process and powder shape and/or coarse-grained interpolation material, and as required from CaO, Ca (OH) ₂, MgO, Mg (OH) ₂In select more than one and it mix after, making packed layer with this slag stacking or in any space, make this slag stacking or packed layer under the condition that carbon dioxide gas exists, carbonation reaction take place, make slag and interpolation material fixed, obtain slag and add material becoming block stone material.This slag is at least a slag of electing from the combination that powder shape slag, coarse grain shape slag and fritter shape slag are formed.This slag also can be through removing powder shape or the coarse-grained slag that iron block is handled.

This form is to be the heavy stone material of using in the river of establishing of primary raw material with the slag that produces in the steel manufacture process, and such slag can be: the blast furnace series slag of blast furnace slow cooling slag, blast furnace water quenching slag etc.; The steel-making series slag of the desiliconization slag that operations such as preliminary treatment stove, converter, casting produce, desulfurization slag, dephosphorization slag, decarburization slag, casting slag etc., ore reduction slag, electric-furnace slag etc., be not limited to these slags, also can mix and use two or more slags.

The slag that produces in the above-mentioned steel manufacture process contains different many (general weight ratio is a few percent to 30%) iron block of the degree composition of iron (granular iron etc.), for the recycling in steel manufacture process of such iron, carry out the recovery of iron block in the slag.Be generally and reclaim iron block and will carry out break process to slag.So comprised just being the slag of powdery, meal shape or little bulk state originally, and the slag of process recovery iron block operation must also be powder shape, coarse grain shape, little bulk.The particle diameter of the slag granules of this recovery iron block operation of general process is the cm order of magnitude or littler (for example 5cm is following).

This form heavy establish the stone material used in the river with at least a in powder shape slag, coarse grain shape slag and the fritter shape slag be raw material.But the slag that adopts among the present invention can be at least a slag in powder shape slag, coarse grain shape slag and the fritter shape slag, not passing through the condition of above-mentioned recovery iron block operation as necessity.

It is heavy when establishing the stone material raw material of using in the river that these slags are used for, and the iron-holder in the general slag is not less than to use through removing slag that iron block handles and also is fine as the situation of the raw material of stone material.It would be better to say that it is good containing an amount of iron (the particularly metallic iron of granular iron etc. and the material of containing metal iron) in slag.This is owing to contain an amount of iron divide moltenly in river in slag, replenishes the iron branch as nutritive salt in the river, and is favourable to the growth of seaweeds.The content weight ratio of iron is being suitable more than 3% in slag for this reason.

According to heavy situation of establishing the river of stone material, existence causes the river oxygen deprivation because of the iron block oxidation that contains in the slag and supplies with in river under the situation of excessive iron branch problem, after the slag that uses removed iron block and handle, raw material as stone material uses, and no longer adds the material of above-mentioned metallic iron and containing metal iron.

The slag that above-mentioned steel manufacture process produces contains the different many iron blocks of degree, and the iron block in such slag also can be handled the iron block that reclaims significant proportion by above-mentioned recovery iron block.General slag composition and iron block are to mix with the state that is interweaved, so generally the break process of carrying out to a certain degree can not fully be removed iron block, after reclaiming the iron block operation, in slag, also a considerable amount of iron blocks can remainingly be arranged in reclaiming the iron block operation for this reason.Therefore when only being located in the river, can produce the problem that the iron block oxidation that contains in the slag causes the river oxygen deprivation and excess supply iron divides in river according to the difference in heavy basin of establishing by stone material that the slag that reclaims behind the iron block is obtained is heavy.So for the stone material that is suitable for such basin, should use through removing iron block and handle, remove the slag of main iron branch and make raw material.

Generally slag composition and iron block are that the state that closely is interweaved mixes in slag, so must when iron block is handled, manage powder shape or coarse grain shape removal iron block (removing) to slag with methods such as magnetic separation, therefore comprise being powdery or coarse-grained slag originally, and must the granular and/or coarse grain shape of pulverize as the slag through removing the iron block operation of raw material.Generally the particle diameter through the slag granules of such removal iron block operation is the mm order of magnitude or littler (for example below the 5mm).

Therefore the heavy stone material of establishing in the river of the present invention is applicable to that the iron that has the river oxygen deprivation and supply with divides the river of superfluous problem in river, be being raw material through removing powder shape that iron block handles and/or coarse-grained slag.

Except inevitable remaining iron block composition, hope will be removed the iron block in the slag as far as possible in removing the iron block processing.Wish that generally iron branch (iron block) content in the slag is lower than percentage by weight 3%.

At least a slag of in this form, selecting in the above-mentioned a pile of forming by powder shape slag, coarse grain shape slag, fritter shape slag, or through removing powder shape that iron block handles and/or coarse-grained slag as main material, the CaCO that in carbonation reaction, generates ₃Or CaCO ₃And MgCO ₃Make its fixed (carbonic acid curing) as binding agent.Heavy to establish the stone material of artificial structure such as stone material, the particularly fish pass used in the river and artificial riverbed using be well-adapted raw material for the stone material used as the riverbed of Kuai Zhuan stone material etc. as can be seen.

The slag that general steel manufacture process produces contains the CaO of a great deal of (being generally percentage by weight 20%～60%), of the present invention sinking established powder shape and/or the coarse-grained slag that the stone material of using in the river is the processing of employing process removal iron block, CaO that contains or the Ca (OH) that is obtained by the CaO variation in slag ₂(comprise CaO, the Ca (OH) that add as required ₂), make it be varied to CaCO by above-mentioned reaction ₃, CaCO ₃Make slag granules (containing under the situation of adding material) be consolidated into block stone material as binding agent for adding material granule and slag granules.

In this external most slag, contain a certain amount of MgO when containing CaO, this form is with heavy the establish stone material in river used of such slag as raw material, MgO or the Mg (OH) that is obtained by the MgO variation ₂(comprise MgO, the Mg (OH) that add as required ₂) make it be varied to MgCO by above-mentioned carbonation reaction ₃, this MgCO ₃And CaCO ₃Make slag granules (containing under the situation of adding material) be consolidated into the stone material that bulk obtains as binding agent for adding material granule and slag granules.

CaO that contains in the slag that produces in steel manufacture process and part or all of MgO, the absorption moisture or the other reasons of process certain hour are transformed into Ca (OH) sometimes ₂And Mg (OH) ₂Deng, above-mentioned this situation is no problem as the slag that utilizes in the present invention, these Ca (OH) ₂And Mg (OH) ₂Also can become CaCO respectively by carbonation reaction ₃And MgCO ₃, can access the heavy stone material of using in the river of establishing of this form.

This form heavy established the stone material of using in the river, and to can be used as the stone material of using in the riverbed, the stone material that fish pass is used etc. heavy if lay and use in water.The form that stone material of the present invention is arranged in the water is arbitrarily, not merely is heavy establishing, and lays also passable regularly at suitable structure position.

The heavy stone material of using in the river of establishing of this form, be particularly suitable for fish pass with the heavy of the artificial structure position of stone material etc. and artificial riverbed etc. if lay, wherein the stone material of using as fish pass is heavy if lay regularly in the bottom of fish pass at least.Position beyond fish pass, for example its structure position arbitrarily also can be laid regularly in top (for example the forming part or all the gently sloping surface at artificial structure position of the head-work of embankment) at the artificial structure position flow through of water and artificial riverbed (for example piling up the riverbed of constructing with penning or stone) of fixedly constructing etc.

Form when this form of use heavy established the stone material of using in the river (size and shape etc.) is arbitrarily, and for example size can be the order of magnitude about from the order of magnitude more than the 1000mm to tens of mm, can suitably select according to purposes.At fish pass and other artificial structure position or during fixing layings such as artificial riverbed, only pile up for construction easily and according to occasion and just to fix laying, hope use block, tabular or watt shape or approximate shapes (setting material) with stone material.Heavy form of establishing is also passable but block non-setting material is only used in the bottom in fish pass.

(a)～(c) of Fig. 9 is expression with stone laying of the present invention or the heavy artificial structure position of fish pass etc. or the topology example of artificial riverbed situation established, and wherein (a) is the fixing example of laying the stone material 40a of bulk or shape such as tabular in the fish pass bottom of tilting.When fixing these stone materials 40a, also can use mortar as required.In this example the stone material face of the plane of disruption 40 (fragmentation or broken-out section) as the bottom surface that constitutes fish pass.This plane of disruption 40 is solidifying fragmentation or the broken-out section that the stone material piece obtain is broken or form when breaking with carbonic acid and since compare with the surface that carbonic acid solidifies concavo-convex significantly, so make organism in water more effective aspect moving easily.(b) of Fig. 9 is that staged fish pass bottom (each ladder) free-standing is laid the example of block stone material 40b.Fig. 9 (c) is a fixing example of laying the stone material 40c of shape such as block or tabular on artificial structure position except that fish pass or artificial riverbed, such structure is as the artificial structure position that can be suitable for beyond the fish pass, for example can enumerate the example of the gently sloping surface etc. of the head-work that constitutes embankment etc.

This form heavy establish the stone material used in the river as heavy if lay the stone material that riverbed etc. uses, following advantage is arranged:

1. (or the Ca (OH) that generates by CaO because the CaO that contains in the slag ₂) major part become CaCO ₃So, can prevent to be dissolved into that the pH value that causes river in the river raises and because the pH value rising around the stone material causes the adhering to of algae, late-blooming problem because of CaO.The pH value of general nature stone (lime stone) is about 9.3, and concrete pH value is about 12～12.5, and the heavy stone material of using in the river of establishing of the present invention utilizes the above-mentioned neutralization reaction can be suitable with natural stone during fabrication, and the pH value is below 10.

2. because powder shape and/or coarse-grained slag solidify the character that overall (surface and inner) of the block that obtains has porous through carbonic acid, therefore water plant such as algae is easily attached to stone surface, and because stone material inside also is cellular, the favourable composition of growth to algae etc. that contains in the stone material is dissolved in the water easily, beneficial to the growth of algae.

3. block slag when establishing the stone material of using in the river and using, is subjected to the restriction of the cooling means and the condition of molten slag as heavy, generally its size has individual boundary (about general maximum 800mm), is difficult to obtain the neat bulk stone material of size.In contrast, react the stone material that solidifies through carbonic acid by powder shape and/or coarse grain shape slag, after solidifying, selection by the shape when carbonic acid solidifies or carbonic acid digs out the selection of shape etc., its big I is adjusted arbitrarily, so also obtain being placed on the bulk stone material used in the river, heavy if lay the middle piece stone material, fritter stone material (broken shape stone material) etc. in riverbed easily, obtain the stone material of size arbitrarily easily.

4. the heavy stone material of using in the river of establishing wishes to use the optimal stone material of density (proportion) according to the situation in riverbed and the situations such as speed of current, this point wishes that powder shape and/or coarse-grained slag are solidified into stone material through the carbonic acid reaction, the bulk density (compacted density) of the slag when solidifying by suitable adjustment carbonic acid can be adjusted its density arbitrarily.

5. heavy the establishing that is obtained by powder shape of handling through the removal iron block and/or coarse-grained slag used under the situation of stone material in the river, owing to removed main iron block, be applicable to the basin of the problem that exists the river oxygen deprivation and divide to the too much iron of river supply, can not produce because of the iron block oxidation and cause river oxygen deprivation and the problem of dividing to the too much iron of river supply.The heavy stone material of using in the river of establishing that is obtained by this slag of removing iron block is arranged again, and it is more relatively that the part of having removed iron block helps the composition that slag carbonic acid solidifies, so favourable to the intensity that guarantees stone material.

6. general because stone material of the present invention is the stone material under fixed stacking or the packed layer cutter, has angular shape, so it is heavy if be laid under the situation in riverbed it, compare with the cobblestone of generally in the river, seeing or the natural stone of analogous shape, be easy to generate big space between the stone material and between stone material and the river bed, this is formed with existence, the resting space of usefulness easily concerning organism in water.

As previously mentioned, the heavy stone material used in the river established of the present invention is in the river purposes, particularly the stone material (the following stone material of using with fish pass is the example explanation) used of artificial structure position of flowing as the water of fish pass etc. and artificial riverbed is suitable especially, have when using the stone material as such purposes following except that the premises advantage.

7. the character that has porous by powder shape and/or coarse-grained slag through the surface that carbonic acid solidifies the block that obtains, have countless concavo-convex, so, go up the organism in water (for example shell-fish and aquatic insect etc.) of moving and also in fish pass, move easily to hook in the riverbed (surface of projections such as stone and water plant) with pawl etc. heavy if when being laid on the fish pass bottom it.Stone material particularly of the present invention has concavo-convex owing to having above-mentioned porous shape surface, and the pH value is also suitable with natural stone, has the active ingredient character of dissolving easily, so water plants such as algae adhere to easily, grow, because the adhering to, grows of such water plant, above-mentioned organism in water is easier to be mobile in fish pass.

When 8. using stone material to use, can only sink in the fish pass and establish block stone material,, wish the stone material of shape such as block or tabular fixedly is laid on bottom the fish pass in order to prevent to run off because of water mobile makes stone material as fish pass.Owing to can make shape arbitrarily when the stone material of powder shape and coarse-grained slag carbonic acid curing is made, obtain block or tabular stone material easily, construct easily so pass through to use such stone material to fix when laying the fish pass bottom, and can lay reliably.

9. compared with former foamed concrete and can reduce construction cost, the pH value is also low owing to comparing with concrete, so good especially to the organism in water of moving along the fish pass bottom.

The heavy stone material used in the river established of the present invention is because the CaCO that the little slag of particle diameter generates by carbonation reaction ₃Or CaCO ₃And MgCO ₃Closely fixed as binding agent, therefore so have enough intensity,, also needn't worry can produce and break and collapse in carrying and heavy if impacted when laying or be placed on for a long time in the water in the river.

The heavy of this form established in the stone material of using in the river, because the corresponding situations of using such as place are taked the composition that suits respectively, can contain various interpolation materials (powder shape and/or coarse-grained interpolation material) simultaneously by powder shape and/or coarse grain shape slag.Add the powder shape of for example adducible powder shape that the soluble silica source arranged of materials or coarse grain shape material (soluble silica, contain the material of soluble silica), iron oxide source or coarse grain shape material (iron oxide, contain the material of iron oxide) as these.

The heavy soluble silica that contains in the stone material of using in the river and the iron oxide established is by being dissolved in the water, and be favourable to the growth of aquatic plants such as algae.

Powder shape or coarse-grained soluble silica are arranged and/or contain the material of soluble silica as the powder shape in soluble silica source or coarse grain shape material.The material that contains soluble silica can use dust that coal combustion such as thermal power station produces and clinker ash etc.Wherein dust weight percentage is about 45～75%, and clinker ash contains the soluble silica of percentage by weight about 50～65%.

Because the blast furnace water quenching slag also contains many soluble silica, part or all of slag used the blast furnace water quenching slag, for example copper smelter slag and blast-furnace slag mix use, also can obtain adding the same effect of situation as the interpolation material in soluble silica source.

Powder shape or coarse-grained iron oxide are arranged and/or contain the material etc. of iron oxide as the powder shape of iron oxide source or coarse grain shape material, the powder shape of the cheapness of getting especially easily or coarse grain shape material be adducible the dust of the iron content that steel manufacture process produces and rolling iron scale etc.The dust of iron content is generally the dust of ironmaking, and such dust Fe conversion contains the iron oxide iron about 75%.Rolling iron scale Fe conversion also contains the iron oxide about 70%.

When expecting the smaller stone material of proportion, compare with other slag that to have at least a part to adopt the smaller water granulated slag of proportion to make main raw material be effective.

The heavy stone material of using in the river of establishing of the present invention has relatively more loose character, therefore can access above-mentioned effect 2..The porosity of stone material does not have specific restriction, generally wishes about 10～70% porosity.

Heavy manufacture method of establishing the stone material of using in the river to this form describes below.

Figure 10 represents the manufacturing process of the inventive method, and Figure 11 represents an example of manufacturing process.The slag that steel manufacture process produces is at first removed iron block and is handled, and removes main iron block composition (abrasive grit).Slag composition and iron block in the general slag are that the state that mutual densification interweaves mixes, remove iron block handle must be the slag pulverize granular or coarse grain shape, therefore generally with disintegrating machine slag being crushed to particle diameter is the mm order of magnitude or littler (for example 5mm is following), removes iron block after the fragmentation and handles.But the particle diameter of slag reaches that to remove the degree that iron block handles just passable, about according to the proterties of slag etc. at the thicker granular iron block of just can removing, just can be broken into the particle diameter that can remove iron block to slag.

Also can reach the natural efflorescence that can remove the iron block degree to particle diameter or the slag under the spheroidizing state is packed into, such slag there is no need to carry out break process.

The general iron block of removing is handled and is adopted magnetic separator etc. to carry out magnetic separation (method of the granular iron in the slag being removed with magnet), but is not limited to this, can use the difference in specific gravity choosing method, for example utilizes the selection by winnowing etc. of the difference in specific gravity of iron block and slag.

Utilize and remove the iron block processing the main iron block composition removal in the slag.

Through removal in the powder shape and/or coarse-grained slag that iron block handles, add material as required, in carbonation reaction necessary CaO, MgO are arranged again in slag under the not enough situation, as required from CaO, MgO, Ca (OH) ₂, Mg (OH) ₂In select more than one to add, mix with slag.As adding material, for example can add the powder shape of the powder shape in soluble silica source or coarse grain shape material (soluble silica, contain the material of soluble silica), iron oxide source or coarse grain shape material (iron oxide, contain the material of iron oxide), CaO etc., concrete example as previously mentioned.

Add the interpolation raw material of material and CaO etc. and the mixed method of slag in addition and can adopt following any method, for example the method that slag of discharging from remove the iron block treatment facility and interpolation raw material are mixed in hopper; In removing the iron block treatment facility, join mixed method in the slag of removing after iron block is handled adding raw material; Method with the mixing of heavy-duty machineries such as excavator; The method of mixing with concrete mixer truck (concrete central mix plant) etc.

For having added material, mixed slag carbonic acid curing, slag be piled up or be filled in any space as required.

When escorial is mounded, also have no relations, but wish to make the carbon dioxide gas that is blown into can be fully mobile in whole stacking with the mode of stacking, and for preventing that slag from because of dispersing and rainwater causes loss, cover stacking with thin plate.

To pile up slag or fill for example can use with dividing plate surround three faces the hole, surround the sandbox of four faces or container etc. with dividing plate.Wherein pile up in the hole or fill the situation of slag also the situation with above-mentioned stacking is identical, hope covers stacking or packed layer with thin plate.Also wish to cover packed layer or case lid is set in the situation of using sandbox or container with thin plate.Figure 11 is illustrated in the situation that forms packed layer A in the sandbox.

The accumulating amount of slag and loading do not have specific restriction, and for example several tons of accumulating amount or the loadings to hundreds of tons of scales are also passable, and it is also passable to the accumulating amount or the loading of tens of blocks of stone materials perhaps to be equivalent to a stone material, can be quantity arbitrarily.But the accumulating amount of slag or loading are that stacking or the packed layer after the carbonic acid curing can be easily broken with heavy-duty machinery at most, easily block stone material is cut a hole to get off to transport, and cut a hole the stone material that gets off to transport by such fragmentation and have the advantage that helps the concavo-convex section that algae adheres to.Therefore the function aspects of the stone material of using from production capacity and as the riverbed etc. wishes slag accumulating amount or loading will arrive to a certain degree more, wishes that specifically its scale is more than 10 tons.

Corresponding to the density of the stone material that will make, hope will be adjusted the stacking of slag or the bulk density of packed layer (compacted density).That is to say that the heavy stone material of using in the river of establishing wishes and will adjust density according to the state in riverbed and current or the like.In addition because gas porosity (porosity) difference of stone material causes the degree of adhering to, growing of algae also different with the situation of dissolving the active ingredient that from stone material inside, also wishing sometimes will be according to the gas porosity of the difference adjustment stone material of the situation in the river of use stone material.

The density of the stone material made from the method for this form is relevant with the stacking of slag or the bulk density of packed layer (compacted density), therefore the degree of the compacting of slag stacking or packed layer to be adjusted according to above-mentioned needs, the density of stone material can be adjusted at an easy rate by adjusting bulk density.

The degree of slag stacking or packed layer compacting is arbitrarily, but common bulk proportion/true specific gravity that is to say that in 0.3～0.9 scope the porosity that will tamp in stacking or the packed layer is 70～10% degree.

The stacking of slag or the compacting of packed layer can be adopted the method for tamping with heavy-duty machinery from the top of stacking or packed layer, and the method that makes stacking or packed layer vibration compacting, when tamping, the bulk density of stacking or packed layer is adjusted by the degree of adjusting compacting.When making the low especially stone material of density, can not tamp yet, slag is piled up or fill after carry out carbonic acid like this and solidify.

When for example the stacking in aforesaid hole, sandbox or container or packed layer being tamped as the concrete grammar of compacting, in advance the inboard of hole, sandbox or container make the expression target volume the sign line, the slag of knowing weight put into their inside after, tamp the height of the above-mentioned sign line of top arrival that makes stacking or packed layer.

After the adjustment of finishing above stacking or the bulk proportion of packed layer, make its stacking or packed layer under the condition that carbon dioxide gas exists, carry out carbonation reaction, slag carbonic acid is solidified.Specifically be blown into carbon dioxide gas or contain the gas of carbon dioxide gas, or stacking or packed layer be placed on carbon dioxide gas or contain under the atmosphere of gas of carbon dioxide gas, slag is carried out carbonic acid solidify to the stacking of slag or packed layer.

The method that is blown into carbon dioxide gas or contains the gas of carbon dioxide gas to stacking or packed layer has no particular limits, and in the bottom of stacking or packed layer device for blowing gas is set, and it is the most effective being blown into gas by such device for blowing gas.Specifically, with suitable configuration density pipe arrangement that air feed uses or flexible pipe etc. are set in the bottom of stacking or packed layer (being their base plate) under situation with hole, sandbox or container, (for example at interval 300mm～400mm) is provided with the gas injection hole, can blow out carbon dioxide gas or contain the gas of carbon dioxide gas from the gas injection hole with suitable spacing on these pipe arrangements or flexible pipe.

In addition as stacking or packed layer being placed on carbon dioxide gas or containing method in the atmosphere of gas of carbon dioxide, can adopt stacking or packed layer are placed on airtight space (comprising container etc.), in this space, supply with carbon dioxide gas or contain the gas of carbon dioxide with state arbitrarily.

As the carbonated gas that uses be fit to for example have emission gases in sodalime factory of integrated iron and steel works (general, CO ₂: about 25%) and the heating furnace emission gases (general, CO ₂: about 6.5%), but also be not limited only to these gases.There is the dense carbon dioxide that can produce carbonated gas to spend problem low and that treatment effeciency reduces again, do not have what special problem in addition.Therefore gas concentration lwevel has no particular limits, but considers to handle effectively to wish that gas concentration lwevel is more than 3%.

The amount of being blown into of carbon dioxide gas or carbonated gas also has no particular limits in addition, so long as it is just passable to blow under the degree that the stacking that does not make slag or packed layer flow, generally can guarantee to be blown into the amount of gas at 0.004～0.5m as standard ³/ mint just.The time (carbonating processing time) that is blown into gas also has no particular limits, and wishes it is carbon dioxide gas (CO as standard ₂) the amount of being blown into be the time more than 3% of slag weight, that is to say the amount that is converted into gas, every 1t material will be supplied with 15m ³Above carbon dioxide gas (CO ₂).

To stacking or packed layer is blown into carbon dioxide gas or carbonated gas can be compared with normal temperature at normal temperatures, being blown into gas under the high temperature is favourable from the ability aspect of reaction only.But because the temperature of gas is too high, CaCO ₃Resolve into CaO and CO ₂, MgCO ₃Resolve into MgO and CO ₂, must be to use the gas temperature that such degree of decomposition does not take place when using high-temperature gas.

Utilize the reaction of CaO, MgO and carbon dioxide gas to make the curing of slag carbonic acid that moisture must be arranged, wish that water content is about 3～10% in the slag before carbonating is handled beginning.This is owing to be dissolved in the result of promotion carbonation reaction in the water by CaO, MgO and carbon dioxide gas.Under the low excessively situation of the slag water content of stacking or packed layer formation, wish in the mixed process of Fig. 6, in slag, to add water, the adjustment that improves the slag water content for this reason.In case carbon dioxide gas or carbonated gas is blown into makes H in the water ₂After O is saturated,, can prevent the drying of slag, promote carbonation reaction by blowing to stacking or packed layer.

The value of the water content of the compressive strength maximum of the block after also can adjusting to the moisture of mixture carbonating and handle.Value evaluation method in this water content is as follows:

(a) for the raw slag of 100 parts of weight, preparation has added the raw slag of water absorption rate water of any amount more than 3 times of raw slag particle.Above-mentioned water absorption rate is the fine aggregate stipulated among JIS A1109 or the A1110 or the water absorption rate of coarse aggregate.

(b) various raw slag are filled in make packed layer in the sandbox, the porosity in the time of making drying is certain.

(c) be blown into a certain amount of 10～40 ℃ humidification carbon dioxide gas to packed layer, carry out the carbonating maintenance of certain hour, raw slag is solidified.

(d) measure the compressive strength of the slag after solidifying, obtained the maximum of compressive strength.The value of corresponding peaked moisture is only amount of moisture.

By in slag stacking or packed layer, supplying with carbon dioxide gas or carbonated gas, as discussed previously, by CaO (or Ca (OH) ₂), MgO (or Mg (OH) ₂) generate CaCO with the reaction of carbon dioxide gas ₃, MgCO ₃, this CaCO ₃Or CaCO ₃And MgCO ₃Become binding agent make slag granules (with add the situation that material mixes under be the particle of slag granules and interpolation material) fixed.

After such carbonic acid curing is finished, with heavy-duty machinery stacking or packed layer are broken into suitable size as required, cutter is broken into the block heavy stone material of using in the river of establishing.Size when therefore breaking according to cutter can obtain the stone material of size arbitrarily.Usually block stone material cutter is broken into the size of 80～1500mm, and the fragmentation when breaking by cutting a hole forms the concavo-convex section that water plant adheres to easily on the stone material.

In the manufacture method of the present invention, because enough little of the volume of packed layer, it is disconnected not carry out above-mentioned cutter, remains untouched to use and be divided into about 2 also passable as the stone material utilization.For example noted earlierly obtain shape stone material such as block or tabular that's how things stand, carry out fragmentation or cut off into 2 piece by carbonic acid being solidified the block stone material obtain this moment, and the stone material of 2 bulks or the shape such as tabular of the plane of disruption (fragmentation or broken-out section) is arranged above obtaining.

Manufacture method of the present invention has following advantage:

1. owing to be that slag carbonic acid is solidified, adjust bulk proportion, heavyly establish in the river density and can adjust simply with stone material by the compacting degree of adjusting stacking or packed layer.As previously mentioned, the heavy stone material of using in the river of establishing wishes and will suitably adjust density and gas porosity according to riverbed and current situation etc., can be arbitrarily and to carry out such adjustment simply be a big advantage of establishing the manufacture method of the stone material of using in the river as heavy.Known the technology of making pelletizing with carbonic acid curing as former technology, the density of adjusting non-processing material in wide scope with such method of making pelletizing is difficult.

2. method of the present invention is that slag carbonic acid is solidified, carbonic acid solidifies the back stacking or packed layer is broken into suitable size, cut a hole into the block stone material of desirable size, or packed layer remained untouched or cut off as block stone material and use, so the size of the stone material under cutting a hole and the size of packed layer are carried out suitable selection, (80～1500mm) stone material for example also obtains the stone material of bulk easily to access any size.Solidify the former technology of making pelletizing particle etc. with above-mentioned carbonic acid, limit is about 30～50mm at most for the size of the block that obtains, and because the disperse of size produces the little block of size inevitably.Therefore method of the present invention can access the boulder material, has tangible advantage as heavy manufacture method of establishing the stone material of using in the river.

When 3. fixing artificial structure positions such as laying fish pass and artificial riverbed with stone material, the stone material that wish to use is the stone material of shape such as block or tabular, with size and the shape of method of the present invention, can obtain such stone material at an easy rate by suitably selecting packed layer.

4. the stacking of slag or packed layer were cut a hole the block stone material that the method for getting block stone material can access the convex-concave surface (section) that has algae and adhere to easily with fragmentations such as heavy-duty machineries by adopting after carbonic acid solidified.Have again that for above-mentioned block or tabular stone material utilization 3. carbonic acid to be solidified the block stone material that obtains broken or cut into 2, have the stone material of the shape such as block or tabular of broken-out section above accessing.

Embodiment 5

Converter slag powder below the granularity 3mm is piled up the 1.5m height in the hole of wide 4m * depth 6m, suitably the compacting back is the hole sealing, by air demand 50Nm ³The ratio of/hr supplies carbon dioxide gas three days, and slag carbonic acid is solidified.Slag heavy-duty machinery fragmentation such carbonic acid solidifies obtains the block stone material that size is approximately 30～250mm, establishes the stone material of using in the river and has enough intensity as sinking.

Embodiment 6

(CaO:54.9% MgO:2.3%) as raw material, has made the fish pass stone material with two kinds of methods of following (1) and (2) the dephosphorization pulverized slag of the weight below the granularity 6mm 100%.

(1) pulverized slag is filled in is of a size of in the sandbox that 50cm * 50cm * 15cm has aeration after the compacting, certain intervals is arranged being placed in the hole between 60 such sandboxes, pressing air demand 70Nm after the sealing of hole ³The ratio of/hr supplies carbon dioxide gas 5 days, and slag carbonic acid is solidified.Take out sandbox then, obtain block fish pass stone material.

(2) pulverized slag is filled in is of a size of in the sandbox that 100cm * 100cm * 50cm has aeration, polyethylene separator (100cm * the 100cm * 2cm of middle opening is loaded onto in the centre position of the wide 100cm of sandbox during filling, opening: 85cm * 85cm), tamp behind the filling slag.Certain intervals is arranged being placed in the hole between 18 such sandboxes, air demand 70Nm is pressed in sealing back, hole ³The ratio of/hr supplies carbon dioxide gas 5 days, and slag carbonic acid is solidified.Take out sandbox then, the block stone material that obtains is divided into 2 sections in the centre position that dividing plate is housed, and has the stone material that the block fish pass of section (broken-out section) is used above obtaining.

The stone material that the block fish pass that above-mentioned (1) and (2) is obtained is used is routed to fish pass bottom based on concrete by the form shown in Fig. 4 (a) respectively.Its section of stone material of using for the fish pass of (2) is laid in the bottom surface of fish pass.Therefore different with the smooth bottom of concrete (concrete block or concrete construction), obtain that the bottom has that shell-fish etc. moves easily because of the loose fish pass that forms concavo-convex rough surface.Particularly state the fish pass part of the stone material of (2) in the use, obtain very concavo-convex fish pass bottom, surface.

Because stone material of the present invention utilizes neutralization reaction during fabrication, have the pH value suitable with natural stone (lime stone), so at the beginning of bringing into use after the fish pass construction of concrete system, because of the composition that dissolves makes surface p H value high, do not find to postpone adhering to of algae, and, find that algae adheres to, grows in the bottom of fish pass in the relatively shorter time because the fish pass bottom that builds up with stone material of the present invention is concavo-convex rough surface because of loosening.

According to the present invention described above, a kind of heavy stone material of using in the river of establishing can be provided, it can not cause the oxygen deprivation of river and the rising of pH value, and the stone material of using as riverbed on the river etc. is heavy if when being laid in the water, good performance can be brought into play in aspects such as growth water plants such as living space that forms fish etc. and algae, there are the artificial structure position such as fish pass of the dykes and dams that are located at the river and embankment etc. and artificial riverbed etc. heavy again if when laying, hydrobiological moving with the development of water plant beyond fish can be brought into play good performance, adds easy adjustment size and density.

Particularly, adopt manufacture method of the present invention, owing to be under the state of stacking or packed layer, to make slag carry out carbonic acid to solidify, so utilize to adjust the degree of stacking or packed layer compacting, suitably select carbonic acid to solidify the size of back cutter stone material down and the size of packed layer etc., can be simply and make any density and the big or small heavy stone material of using in the river of establishing at low cost.Particularly will transform the riverbed needs a large amount of stone materials, adopts words of the present invention, compares with concrete with using nature stone as the heavy stone material of establishing usefulness, can obtain stone material at low cost, can cut down the engineering cost of transforming the riverbed.

The character of the efflorescence that the expansion that has the phase change expansion of the γ-attitude calcium-silicate that generates in when cooling and produce because of the hydration of free CaO in slag etc. causes, the slag of so in the past efflorescence is difficult to effectively utilize, so in the present invention atomized slag also can utilize as raw material, so this also is very useful invention from the aspect that can effectively utilize the slag that steel manufacture process produces.

The manufacture method of algae field

The inventor is conceived to the fertility of seaweeds of existing algae field so that the breeding effect, utilizing existing algae field that the seedling of seaweeds to basement rock gives birth to and fertility, that is to say the basement rock material that will make algae field usefulness is placed in the existing algae field temporarily, the seedling that makes seaweeds on the surface of material naturally give birth to, grow, obtained the conception that this material is utilized as the basement rock that will make algae field usefulness.Show with this result who is contemplated that the basis is tested and studied, materials such as stone material be placed in the existing algae field that seaweeds on its surface and given birth to and growth in the relatively shorter time; In addition the material of the such seaweeds of fertility is displaced to the place that will make the algae field as kind of material, simultaneously at some new materials of its placed around (seaweeds not the material of giving birth to), in the relatively shorter time, breed on the seaweeds material around of kind material, can form the seaweeds colony that constitutes the algae field.

For the material of basement rock as the manufacturing algae field that contains above-mentioned kind of material, study with regard to the material and the proterties that are suitable for, consequently rest on the weight in seabed if in ocean current etc., do not flow as material, basically without tubing matter and character, wish to have as far as possible the surface texture that the sporozoite that makes seaweeds and seed etc. adhere to easily, that is to say that the surface goes up concavo-convex and stone material projection will be arranged; Wherein to use as material be fit closely to the block artificial stone material of particularly slag that produces in the steel manufacture process being made with specific method, can bring into play good acting on aspect the fertility of seaweeds etc.

The feature of this form is as follows:

Build or transform the method for algae field, it is characterized by: the interim heavy material that constitutes by weight of establishing in existing algae field, after making seaweeds life, fertility on the surface of this material this material is fetched, this material is displaced to as kind of material will builds the place that the algae field maybe will make seaweeds breeding, simultaneously configuration makes seaweeds the other materials of giving birth to around this kind material, and the seaweeds of above-mentioned kind material is bred on above-mentioned other the material.

Wish to adopt following artificial stone material as above-mentioned material:

(a) slag that produces with steel manufacture process is the stone material of primary raw material, the CaCO that slag is generated in carbonation reaction ₃As binding agent, make above-mentioned slag be consolidated into block artificial stone material.This slag is at least a slag of electing in the group of powder shape slag, coarse grain shape slag and fritter shape slag composition.This slag also can be through removing powder shape or the coarse-grained slag that iron block is handled.

(b) slag that produces with steel manufacture process is the stone material of primary raw material, is with the CaCO that generates in the carbonation reaction ₃And MgCO ₃As binding agent, make above-mentioned slag be consolidated into block artificial stone material.But comprise MgCO ₃Situation as hydrate, hydroxide or double salt existence.This slag is at least a slag of electing in the group of powder shape slag, coarse grain shape slag and fritter shape slag composition.This slag also can be through removing powder shape or the coarse-grained slag that iron block is handled.

(c) slag that produces with steel manufacture process and powder shape and/or the coarse-grained interpolation material stone material that is primary raw material is with the CaCO that generates in the carbonation reaction ₃As binding agent, make above-mentioned slag and add mixtures of material to be consolidated into block artificial stone material.This slag is at least a slag of electing in the group of powder shape slag, coarse grain shape slag and fritter shape slag composition.This slag also can be through removing powder shape or the coarse-grained slag that iron block is handled.

(d) slag that produces with steel manufacture process and powder shape and/or the coarse-grained interpolation material stone material that is primary raw material is to be used in the CaCO that generates in the carbonation reaction ₃And MgCO ₃As binding agent, make above-mentioned slag and add mixtures of material to be consolidated into block artificial stone material.But comprise MgCO ₃Situation as hydrate, hydroxide or double salt existence.This slag is at least a slag of electing in the group of powder shape slag, coarse grain shape slag and fritter shape slag composition.This slag also can be through removing powder shape or the coarse-grained slag that iron block is handled.

The method of this above-mentioned form can be applicable to that also the place of being failed gradually in the algae field improves (cultivating the algae field) except the algae field is made in the place that disappears in the place that can not generate the algae field naturally and algae field.

Describe the method (or method of improvement) of the manufacturing algae field of this form below in detail.

In this form, at first be located at existing algae field (special hope is natural algae field) will sink temporarily as the material of kind of material.Existing algae field, particularly natural algae field is compared with the place that can not form the algae field naturally, have the easily environment of breeding (environment such as the light of domination seaweeds fertility, water quality, ocean current) of seaweeds, and also be the place of the high density existence of the seaweeds sporozoite (spore) of emitting and seed in the algae field.Therefore existing algae field be seaweeds at the material surface nature give birth to, the best place of fertility.

The heavy material that is located at above-mentioned algae field rests on the weight in seabed if do not flow in ocean current etc., basically without tubing matter and character.As material no matter be what material, so long as proportion surpasses 1 weight, for example lithotome, artificial stone material (comprising block slag, concrete block etc.), metal material (for example steel and foundry goods etc.), plastics or these composite etc.Its form also has no particular limits, bulk, cuboid, brick-shaped, tabular, even pack into a plurality of blocks in the basket neutralization net as a material etc., can adopt form easily.

The surface of material has concavo-convex and projection is adhered to the sporozoite of seaweeds and seed easily, and taking root of the young might as well.Material is under the situation of stone material etc., wishes to form concavo-convex surface by broken-out section when material fragmentation.Because it is concavo-convex that the broken-out section of stone material etc. forms numerous size, the sporozoite of seaweeds and seed etc. adhere to the fertility of the young well.

Artificial stone material to special hope is elaborated below.

For situation in basket neutralization net that block etc. is packed into,,, wish to wrap, or in advance the means (steel wire rope etc.) that are used for upwards drawing are installed with the net that upwards draws in order to reclaim easily later on when this material is heavy temporarily when being located at the algae field as a material.

Be located at algae field period material is temporarily heavy, the seaweeds sporozoite and the seed that are selected in as far as possible enliven the period of emitting algae the field in.The interim heavy material surface of establishing in the algae field, generally at several months～1 year left and right sides seaweeds give birth to, fertility, grow fast just can become the to grow up to adult that can produce sporozoite and seed or approximate state.As previously mentioned, existing algae field (particularly natural algae field) is aspect environment and the aspect that exists in a monastic silence of the sporozoite of seaweeds and seed, seaweeds is best place in material surface breeding, and the seaweeds of growing in therefore can be during relatively shorter is taken root at material surface.

Seaweeds material surface such give birth to, stage of fertility, this material is pulled out recovery from the algae field.Then the seaweeds of surface fertility is lived and move the place (or the place is transformed in the algae field) of building the algae field to, set, simultaneously the heavy new material (will make seaweeds the other materials of giving birth to) of establishing around this kind material as kind of material is heavy again.For example have 1～2 ratio to place kind of a material with the 10m * 10cm left and right sides scope this moment, sinks with the form of closeer state configuration new material on every side at it and establish material.Have again and will erect the basement rock of stacking new material, plant material put into wherein or be placed among the basement rock all can, also comprise such case in the form of establishing new material sinking around kind of the material in the method for the present invention.

The place that build general algae field is that depth of water 20m is with interior seabed, above-mentioned construction operation can be undertaken by following order, for example the seaweeds that ships with cargo ship is not having living new material to sink to the seabed, builds the basement rock of algae field, hangs the material of sowing then in this basement rock.

The material of the new heavy material of establishing and proterties, form are with above-mentioned identical as the material of kind of material.Also can use the new heavy material of establishing material different and proterties, form with planting material.

Adopt such algae field method of construction, sporozoite of emitting from the seaweeds of kind of material and seed etc. attached to around material on, material around generally in nearly 1 year short-term also has seaweeds living, fertility, can form the colony of the seaweeds that constitutes the algae field.Therefore to sink to establish in the whole place of wanting to build the algae field and will make seaweeds the material of giving birth to, by disperseing heavyly to establish above-mentioned kind material therein, also can build large-scale algae field in short-term simply simultaneously.

This method of this form is with each advantage of previous method, can be described as a method that has by building algae field advantage simultaneously.That is to say method of the present invention since be on the material of the kind material that utilizes the breeding of seaweeds to act on will to build the algae field in existing algae field seaweeds to give birth to, fertility, so the method for being transplanted on the material with the former seedling seaweeds is identical, can guarantee seaweeds is taken root on material, therefore compare with the algae field method of construction that does not have maintenance, can be in short-term and more surely make marine alga breeding, build up the algae field, and have the wide advantage of range of choice of building place, algae field.

In addition, the method of this form since on the environment of algae field be the germination of seaweeds, the only place of growing up made seaweeds on material give birth to, fertility, grow up good and take root good at the seaweeds of material surface fertility, therefore with in the method for construction algae field before the seedling of transplanting seaweeds on the material compare, the existence of seaweeds, the probability of fertility want high, and also have a big advantage, need the growth management after the transplanting resemble the previous method hardly.

On the other hand, method of this form and former nothing safeguard that the method difference of building the algae field only is, be located at existing algae field will sink temporarily as the material of kind of material, be displaced to after the recovery on the place this point of building the algae field, almost there is no need to carry out other manual operation and the growth management of marine alga, therefore we can say similar simple and low-cost of construction algae field method that the method tool being and not being of this form safeguards.

The material that the method that is fit to this form is adopted describes below.

The material that adopts in this form of being adapted at (plant material and build the material that algae field basement rock is used) is the slag that produces with the steel manufacture process stone material as primary raw material, is to be used in the CaCO that generates in the carbonation reaction ₃Or CaCO ₃And MgCO ₃As binding agent, make above-mentioned slag be consolidated into block artificial stone material.The stone material that such bulk is built algae field usefulness can not cause seawater oxygen deprivation and the rising of pH value, and can find in the development of seaweeds etc. good effect is arranged.

Block artificial stone material is like this pressed desired density powder shape slag or accumulation of coarse grain shape slag or filling, under the condition that carbon dioxide gas exists carbonation reaction takes place by this stacking or packed layer, the fixed method of powder shape or coarse grain shape slag can more easily be made, stone material with such method manufacturing can be adjusted to density and size arbitrarily according to the seabed that will use and the situation of ocean current, also is very easy to obtain the stone material of bulk.

Specifically above-mentioned artificial stone material has following advantage:

Owing to removed main iron block composition (abrasive grit), so can not cause causing the seawater oxygen deprivation because of the oxidation of iron block.

(or the Ca (OH) that generates by CaO because the CaO that contains in the slag ₂) major part become CaCO ₃So, can prevent to raise because of CaO causes the pH value of seawater.

Powder shape and/or coarse-grained slag solidify the block obtain through carbonic acid overall (surface and inner) has the character of porous, therefore marine alga is easily attached to stone surface, and, the composition (soluble silica and the iron for example talked about later grade) that can effectively promote seaweeds to grow that contains in the stone material is dissolved in the seawater easily because stone material inside also is cellular.Therefore remain untouched situation about using with stone material as the algae field and compare as the goods of the concrete system of aggregate of block slag, the effect of the growth of promotion seaweeds is arranged with slag.

Particularly seaweeds living, fertility to the interim heavy material that is located in the existing algae field in the method for this form, with must promote seaweeds and build the material breeding and the fertility of planting in the place, algae field around the material, the fertility of the seaweeds young that particularly will promote effectively at material surface to being configured in.In this, because the individuality of seaweeds is effective more the closer to stone material, particularly effective more to the fertility of the young of seaweeds, can effectively promote the growth of the seaweeds young from above-mentioned algae field with being dissolved into active ingredient in the water the stone material, more can improve the effect of the inventive method.

Under the situation of block slag as the use of algae field stone material, be subjected to the restriction of the cooling means and the condition of molten slag, generally its size has individual boundary (about general maximum 800mm), is difficult to obtain the neat bulk stone material of size.In contrast, react the stone material that solidifies through carbonic acid by powder shape and/or coarse grain shape slag, dig out the selection of shape etc. after selection by the shape when carbonic acid solidifies or carbonic acid solidify, its big I is adjusted arbitrarily, also obtains easily as the algae field with special bulk stone materials of wishing such as stone materials.

The stone material of optimal density (proportion) is wished to use according to situations such as seabed and ocean currents with stone material in the algae field, for example establishes under the situation of the big stone material of density in that the seabed that mud is piled up is heavy, and stone material sinks in the mud, does not have the effect of the basement rock of algae field usefulness.By the stone material that powder shape and coarse grain shape slag solidify through the carbonic acid reaction, the bulk density (compacted density) of the slag when solidifying by suitable adjustment carbonic acid can be adjusted its density arbitrarily.

As the adducible blast furnace series slag that blast furnace slow cooling slag, blast furnace water quenching slag etc. are arranged of the slag of the primary raw material of above-mentioned artificial stone material; The steel-making series slag of the decarburization slag that operations such as preliminary treatment stove, converter, casting produce, dephosphorization slag, desulfurization slag, desiliconization slag, agglomeration slag etc., ore reduction slag, electric-furnace slag etc., be not limited to these slags, also can mix and use two or more slags.

The slag that general steel manufacture process produces contains the CaO of a great deal of (being generally percentage by weight 20%～60%), and above-mentioned artificial stone material is CaO that contains in powder shape and/or the coarse-grained slag or the Ca (OH) that is obtained by the CaO variation ₂(comprise CaO, the Ca (OH) that add as required ₂), make it be varied to CaCO by above-mentioned carbonation reaction ₃, this CaCO ₃It is block as binding agent slag granules (containing under the situation of adding material for adding material granule and slag granules) to be consolidated into.

Contain a certain amount of MgO when in most slag, containing CaO, with the above-mentioned artificial stone material of such slag as raw material, MgO or the Mg (OH) that obtains by the MgO variation ₂(comprise MgO, the Mg (OH) that add as required ₂), make it be varied to MgCO by above-mentioned carbonation reaction ₃, this MgCO ₃And CaCO ₃It is block as binding agent slag granules (containing under the situation of adding material for adding material granule and slag granules) to be consolidated into.

Artificial stone material is because the CaCO that the little slag of particle diameter generates in carbonation reaction ₃Or CaCO ₃And MgCO ₃As binding agent is closely fixed, so enough intensity is arranged, even therefore heavyly impacted when establishing in carrying with to marine, and also need not worry to produce in marine long-time placement and breaks and collapse.

The situation in the corresponding marine site of using of artificial stone material is taked the composition that suits respectively, can contain various interpolation materials (powder shape or coarse-grained interpolation material) on the basis of powder shape and/or coarse-grained slag.For example these add the powder shape of the adducible powder shape that the soluble silica source arranged of materials or coarse grain shape material (soluble silica, contain the material of soluble silica), iron oxide source or coarse grain shape material (iron oxide, contain the material of iron oxide), powder shape or coarse-grained CaO etc.Artificial stone material is contained as the CaO that adds material, must make the CaO that contains in the slag or slag is had a mind to the CaO that adds want some as remaining down as the CaO that has neither part nor lot in reaction behind carbonation reaction at least in them.

The soluble silica and the iron oxide that are contained in the artificial stone material are favourable to the growth of seaweeds by dissolving in seawater.Become the seabed and form the phosphorus of red tide reason and form under the many situations of the sulfur content of Kuroshio reason, contain a spot of CaO in the heavy stone material that is located at marine usefulness and can adsorb p and s, have the effect that prevents to produce red tide and Kuroshio.As previously mentioned, in stone material, contain under the situation of a large amount of CaO, have the problem of the pH value rising that makes seawater, adsorb p and s, just much of that at carbonic acid because of changing the remaining a spot of CaO in back.

Powder shape or coarse-grained soluble silica are arranged and/or contain the material of soluble silica as the powder shape in soluble silica source or coarse grain shape material.The material that contains soluble silica can use dust that coal combustion such as thermal power station produces and clinker ash etc.Wherein to contain percentage by weight be about 45～75% soluble silica to dust, and clinker ash contains the soluble silica of percentage by weight about 50～65%.

Because the blast furnace water quenching slag also contains many soluble silica, part or all slag uses the blast furnace water quenching slag, for example copper smelter slag and blast furnace water quenching slag mix to use, and the situation of adding as the interpolation material in soluble silica source also can obtain same effect.

Powder shape or coarse-grained iron oxide are arranged and/or contain the material of iron oxide as the powder shape of iron oxide source or coarse grain shape material, cheap powder shape of getting especially easily or coarse grain shape material be adducible the dust of the iron content that steel manufacture process produces and rolling iron scale etc.The dust of iron content is generally the dust of ironmaking, and such dust Fe conversion contains the iron oxide about 75%.Rolling iron scale Fe conversion also contains the iron oxide about 70%.

As previously mentioned, establish under the situation of heavy stone material in that the seabed that mud is piled up is heavy, stone material can sink in the mud, can occur not having as the effect of algae field with stone material.Therefore the stone material that uses in the marine site that this mud is piled up is wished with the smaller slag of proportion as main raw material, and specifically, using a part to compare the smaller water granulated slag of proportion with other slags at least, to make main raw material be effective.

Above-mentioned artificial stone material has the proterties of porous, therefore obtains aforesaid effect.The porosity of stone material has no particular limits, and wishes that generally porosity is about 10～70%.

Above-mentioned artificial stone material be adopt with to be the manufacture method of base description the heavy stone material that is located at marine usefulness identical method manufacturing from Fig. 5 to Fig. 8.

Embodiment 7

Flow into mortar in the sandbox that is of a size of 1.5m * 1.5m * 1.5m, the concrete block after the sclerosis is cut into 2 with disintegrating machine (rock cutting machine), obtain having marine alga easy the broken-out section of giving birth to various materials with and build the stone material that algae field basement rock is used.

Above-mentioned 1 stone material is transported to the sea of natural algae field, and packing into promotes in the net of usefulness, upwards interim heavy being located in the algae field of the broken-out section of stone material.The heavy seaweeds of electing natural algae field period as of establishing this stone material will be emitted the period before the sporozoite, in order to cover the surface of stone material before the spore of seaweeds etc. adheres at marine precipitum, has selected the seaweeds of this algae field to emit sporozoite September before.After about 1 year, can confirm that seaweeds in the fertility of the surface of above-mentioned stone material, also can stably take root, this stone material be pulled fetch then, it directly is transported to the place of building the algae field as the kind material of building algae field usefulness.

Consider water quality and ocean current etc. as the place of building the algae field, the selected seabed of leaving existing algae field depth of water 4m enough far away.Build in the place of algae field in the about 10m scope of diameter at this, heavyly establish 20 new stone materials that do not have seaweeds and give birth to, broken-out section up simultaneously therein the heart sink again and establish above-mentioned kind material.

Place to this algae field of building after about 1 year is investigated, its result shows that seaweeds breeds on all stone materials around kind of the material, can be confirmed to be abundant fertility.Crop investigation methods with harvesting one level ground is investigated, and its result is 521g/m for having given birth to weight in wet base ²Seaweeds.

Embodiment 8

Converter slag powder below the granularity 3mm is piled up the 1.5m height in the hole of wide 4m * depth 6m, suitably the compacting back is the hole sealing, by air demand 50Nm ³The ratio of/hr supplies carbon dioxide gas three days, and slag carbonic acid is solidified.The slag that such carbonic acid solidifies is cut apart with the heavy-duty machinery fragmentation, obtain 15 as kind of material with or construction algae field basement rock use, size is approximately the block stone material of 1.0～1.5m.

Identical with the foregoing description 3, above-mentioned 1 block stone material is transported to the sea of natural algae field, packing into promotes in the net of usefulness, interim heavy being located in the algae field.The heavy seaweeds of electing natural algae field period as of establishing this stone material will be emitted the period before the spore, in order not cover the surface of stone material before the spore of seaweeds etc. adheres at marine precipitum, has selected the seaweeds of this algae field to emit September before the sporozoite.After about 1 year, can confirm that seaweeds in the fertility of the surface of above-mentioned stone material, also can stably take root, this stone material be pulled fetch then, it directly is transported to the place of building the algae field as the kind material of building algae field usefulness.

Identical with the foregoing description 3, build the place of algae field selected marine site and the depth of water identical with the foregoing description 3.In the about 10m scope of diameter, heavy establish 14 new stone materials that do not have seaweeds and give birth in this place of building the algae field, the heart sinks and establishes above-mentioned kind material therein simultaneously.

Place to this algae field of building after about 1 year is investigated, its result shows that seaweeds breeds on all stone materials around kind of the material, can be confirmed to be abundant fertility.Crop investigation methods with harvesting one level ground is investigated, and its result is 689g/m for having given birth to weight in wet base ²Seaweeds.

When adopting aforesaid the inventive method to build the algae field, the construction place range of choice of algae field is wide, and can be laborsaving and low-cost, can guarantee to build up the algae field in relatively shorter period, and also build large-scale algae field easily.

The feasibility of utilizing on the industry

Adopting above-mentioned the present invention, only is to adopt solid particle aggregates such as holding facile and very cheap slag and concrete, to the CO in the emission gases of industrial process generation₂Can form in commercial quantity, effectively absorb and remove, can effectively reduce CO₂Discharge capacity in the atmosphere. Attaching copper smelter slag in the iron and steel slag that can be only the national steel ironworks be produced as CO₂Absorbent (solid particle aggregate) use, suppose in the applicable situation of the present invention of emission gases that produces with the national steel ironworks, can reduce producing CO ₂1% of amount. The CO of this minimizing₂Amount is as previously mentioned for the reduction target from " the production process energy consumption reduce than nineteen ninety 10% " of master game plan in the iron and steel industry, may cut down significant proportion at this in 10%, with nineteen ninety-five ratio may mean and be equivalent to cut down 24%, can be described as very usefully, and is epoch-making invention.

Utilize the present invention not only can cut down the CO of industrial process etc.₂Amount, and it is wide to build the range of choice of algae field according to the present invention, and can be laborsaving and low-cost, within relatively shorter period, can guarantee to build up the algae field, and build easily large-scale algae field.

Claims (40)

1. the bulk material of a sinking in water, this bulk material is used for cultivating seaweed class and aquatile, and the porosity of this bulk material is 10% to 70%, and this bulk material is by the method production that may further comprise the steps:

(a) mixture of the granular slag composition that produces in the preparation steel manufacture process; And

(b) this mixture is carried out carbonating and handle, generate carbonate, make the said mixture consolidated block as adhesive with the carbonate that generates.

2. the bulk material of sinking as claimed in claim 1 in water is characterized in that the basicity of the slag mixture that produces in the described steel manufacture process is according to CaO/SiO ₂Weight ratio be at least 1.5.

3. method of producing the bulk material of sinking in water, this bulk material is used for cultivating seaweed class and aquatile, and described method comprises following operation:

(a) mixture of the granular slag composition of preparation steel manufacture process generation;

(b) form packed layer by mixture, the bulk proportion of described packed layer/true specific gravity ratio is 0.3 to 0.9; And

(c) mixture in this packed layer is carried out carbonating and handle, make the said mixture consolidated block.

4. the method for the bulk material of production sinking as claimed in claim 3 in water is characterized in that, the basicity of the slag mixture that described steel manufacture process produces is according to CaO/SiO ₂Weight ratio be at least 1.5.

5. the bulk material of sinking as claimed in claim 1 in water is characterized in that described bulk material is used for sinking in seawater.

6. the bulk material of sinking as claimed in claim 1 in water is characterized in that described bulk material is used for sinking in the river.

7. the bulk material of sinking as claimed in claim 1 in water is characterized in that described mixture comprises the granular slag that contains CaO, and described carbonate is CaCO ₃

8. the bulk material of sinking as claimed in claim 1 in water is characterized in that described mixture includes the granular slag of CaO and MgO, and described carbonate comprises CaCO ₃And MgCO ₃

9. the bulk material of sinking as claimed in claim 1 in water is characterized in that, the granular slag mixture that produces in the described steel manufacture process comprises the blast furnace water quenching slag.

10. the bulk material of sinking as claimed in claim 1 in water is characterized in that, the granular slag mixture that produces in the described steel manufacture process comprises through removing the granular slag that metallic iron is handled.

11. the bulk material of sinking as claimed in claim 1 in water is characterized in that, described mixture also comprises granular interpolation material.

12. the bulk material of sinking as claimed in claim 11 in water is characterized in that, described granular interpolation material comprises iron oxide.

13. the bulk material of sinking as claimed in claim 11 in water is characterized in that, described granular interpolation material comprises the material that contains iron oxide.

14. the bulk material of sinking as claimed in claim 11 in water is characterized in that, described granular interpolation material comprises metallic iron.

15. the bulk material of sinking as claimed in claim 11 in water is characterized in that, described granular interpolation material comprises the material of containing metal iron.

16. the bulk material of sinking as claimed in claim 11 in water is characterized in that, described granular interpolation material comprises soluble silica.

17. the bulk material of sinking as claimed in claim 11 in water is characterized in that, described granular interpolation material comprises the material that contains soluble silica.

18. the bulk material of sinking as claimed in claim 11 in water is characterized in that, described granular interpolation material comprises CaO.

19. the method for the bulk material of production sinking as claimed in claim 3 in water is characterized in that, the step that forms packed layer comprises that forming mixture piles.

20. the method for the bulk material of production sinking as claimed in claim 3 in water is characterized in that described bulk material is used for sinking in seawater.

21. the method for the bulk material of production sinking as claimed in claim 3 in water is characterized in that described bulk material is used for sinking in the river.

22. the method for the bulk material of production sinking as claimed in claim 3 in water is characterized in that, the granular slag mixture that produces in the described steel manufacture process comprises the blast furnace water quenching slag.

23. the method for the bulk material of production sinking as claimed in claim 3 in water is characterized in that, the granular slag mixture that produces in the described steel manufacture process comprises through removing the granular slag that metal is handled.

24. the method for the bulk material of production sinking as claimed in claim 3 in water is characterized in that described mixture also comprises granular interpolation material.

25. the method for the bulk material of production sinking as claimed in claim 24 in water is characterized in that, described granular interpolation material comprises iron oxide.

26. the method for the bulk material of production sinking as claimed in claim 24 in water is characterized in that, described granular interpolation material comprises the material that contains iron oxide.

27. the method for the bulk material of production sinking as claimed in claim 24 in water is characterized in that, described granular interpolation material comprises metallic iron.

28. the method for the bulk material of production sinking as claimed in claim 24 in water is characterized in that described granular interpolation material comprises the material of containing metal iron.

29. the method for the bulk material of production sinking as claimed in claim 24 in water is characterized in that, described granular interpolation material comprises soluble silica.

30. the method for the bulk material of production sinking as claimed in claim 24 in water is characterized in that, described granular interpolation material comprises the material that contains soluble silica.

31. the method for the bulk material of production sinking as claimed in claim 24 in water is characterized in that, described granular interpolation material comprises CaO.

32. the method for the bulk material of production sinking as claimed in claim 3 in water is characterized in that the step of described preparation mixture comprises mixing:

(i) the granular slag that produces in the steel manufacture process; And

(ii) from by CaO, Ca (OH) ₂, MgO and Mg (OH) ₂At least a compound of selecting in the group of forming.

33. the method for the bulk material of production sinking as claimed in claim 3 in water, it is characterized in that the step of described preparation mixture comprises: the value of the moisture of mixture being adjusted to the water content of the compressive strength maximum that makes the block that forms after the carbonating processing.

34. the method for the bulk material of production sinking as claimed in claim 3 in water is characterized in that, the described step of mixture consolidated block that makes comprises: the mixture in packed layer is blown into carbonated gas.

35. the method for the bulk material of production sinking as claimed in claim 3 in water is characterized in that, the described step of mixture consolidated block that makes comprises: the mixture in the packed layer is placed on is in the carbonated atmosphere.

36. the method for the bulk material of production sinking as claimed in claim 35 in water is characterized in that, described carbon dioxide comprises and being blown in the water so that H ₂The carbon dioxide that O is saturated.

37. the method for the bulk material of production sinking as claimed in claim 3 in water comprises that also the block mixture that step (c) is generated is broken into the size of 80mm to 1500mm.

38. a method that is used to repair the riverbed comprises: with the bulk material sinking of a plurality of sinkings as claimed in claim 1 in water in comprising hydrobiological water body.

39. the bulk material of production sinking as claimed in claim 1 in water is characterized in that the particle size of described slag is 5cm to the maximum, iron-holder is at least 3wt%.

40. the bulk material of production sinking as claimed in claim 1 in water, its pH value is 10 to the maximum.

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