CN101939269A

CN101939269A - The concrete composition that the carbon footprint reduces

Info

Publication number: CN101939269A
Application number: CN2009801011477A
Authority: CN
Inventors: B·R·康斯坦茨; A·扬斯; T·霍兰德
Original assignee: Calera Corp
Current assignee: Arilake
Priority date: 2008-10-22
Filing date: 2009-10-22
Publication date: 2011-01-05
Anticipated expiration: 2029-10-22
Also published as: EP2352706A4; CA2694988C; CN101939269B; WO2010048457A1; AU2009287466A1; AU2009287466B2; AU2010246393A1; CA2694988A1; EP2352706A1

Abstract

The invention provides concrete composition and preparation and using method that the carbon footprint reduces.The aspect of the concrete composition that described carbon footprint reduces comprises CO ₂Cut and deposit carbonate cpds, it can be present in described concrete water cement and/or the aggregate component.The concrete composition that described carbon footprint reduces can be used in the multiple application, comprises being used in multiple material of construction and the Application in Building.

Description

The concrete composition that the carbon footprint reduces

Cross reference

The application is the " CO by name that submitted on September 30th, 2009 ₂-Sequestering FormedBuilding Materials " the part continuation application of U.S. Patent application 12/571,398, " the CO by name that submits to its on September 30th, 1 ₂Sequestration " " CO by name that submits on U.S. Provisional Patent Application October 31 in 61/101,631,2008 ₂-SequestrationFormed Building Materials " " CO by name that submits on U.S. Provisional Patent Application February 3 in 61/110,489,2009 ₂-Sequestration Formed Building Materials " U.S. Provisional Patent Application 61/149,610 and the " CO by name that submitted on September 25th, 2009 ₂-Sequestration Formed Building Materials " the rights and interests of U.S. Provisional Patent Application 61/246,042, its each be attached to by reference herein and it required to enjoy priority separately.The application also requires the U.S. Provisional Patent Application 61/107 of " the Low-CarbonFootprint Carbon Compositions " by name of submission on October 22nd, 2008,645, the U.S. Provisional Patent Application 61/116 of " the Low-Carbon Footprint Carbon Compositions " by name that submitted on November 19th, 2008,141, the U.S. Provisional Patent Application 61/117 of " the Low-Carbon Footprint Carbon Compositions " by name that submitted on November 24th, 2008,542, the U.S. Provisional Patent Application 61/148 of " the Low-Carbon Footprint CarbonCompositions " by name that submitted on January 29th, 2009,353, the U.S. Provisional Patent Application 61/149 of " the Low-Carbon Footprint Carbon Compositions " by name that submitted on February 3rd, 2009,640, the U.S. Provisional Patent Application 61/225 of " the Low-Carbon FootprintCarbon Compositions " by name that submitted on July 15th, 2009,880, the U.S. Provisional Patent Application 61/234 of " the Methods and Systems for Treating Industrial Waste " by name that submitted on August 14th, 2009,251 rights and interests, it respectively is attached to by reference herein and it is required to enjoy priority separately.

Background of invention

Concrete is most popular in the world engineering materials.According to estimates, present global concrete consumption is annual 11000000000 tonnes of (Concrete, Microstructure, Propertiesand Materials (2006, McGraw-Hill)).This term of concrete be meant glued medium (binding medium) and be embedded in wherein particles of aggregates or the matrix material of fragment.In the most of structural concretes that adopt at present, glued medium is formed by the mixture of water cement and water.

Nowadays most of water cements of Cai Yonging based on be portland cement.Portland cement is mainly made driving away carbonic acid gas and main component is combined into chemical mode in the pyroprocess of new compound by Wingdale, some clay mineral and gypsum.Firing the required energy of described mixture is 1 ton of about 4GJ of cement consumption of every generation.

Because cement manufacturing processed self and generation power all generate carbonic acid gas with the energy plant that moves described manufacturing processed, so the cement manufacturing is the main source of current carbonic acid gas airborne release at present.According to estimates, the carbonic acid gas of cement mill discharging accounts for 5% of carbonic acid gas global emissions.Along with the hope that becomes increasingly conspicuous and reduce carbon dioxide discharging (major cause of Global warming) of Global warming and ocean acidifying problem exists, the cement process industry will be subjected to more and more stricter examination.

The fossil oil that adopts in the cement mill comprises coal, Sweet natural gas, oil, old tire, Municipal waste, refinery coke and biofuel.The biofuel that fuel also derives from tar sand, resinous shale, coal liquid and gasification and makes by synthetic gas.The cement mill is CO ₂A main source of discharging wherein discharges from the burning of fossil oil and makes Wingdale, shale and other compositions become the CO that calcining discharged of portland cement ₂The cement mill also produces used heat.The cement mill also produces other pollutents such as NO in addition _X, SO _X, VOCs, particulate matter and mercury.The cement mill also produces cement flue Dust (CKD), the necessary sometimes landfill of CKD, and normal landfill is in the objectionable impurities landfill yard.

Carbonic acid gas (CO ₂) to be confirmed to be the main arch-criminal of Global warming and ocean acidifying phenomenon in discharging.CO ₂Be the incendiary by product, bring operation, economy and environmental problem.Estimate CO ₂To facilitate more substantial heat-storage in atmosphere with the rising of the atmospheric concentration of other greenhouse gases, thereby cause the rising of surface temperature and climate change fast.CO ₂Also interact with the ocean always, ocean pH is fallen to 8.0.CO ₂Monitoring shows, Atmospheric CO ₂Risen to about 380ppm of today from about 280/1000000ths (280ppm) of the 1950's, and expectation will be above 400ppm in next ten years.It is deleterious on costliness and the environment that the influence of climate change is likely economically.The potential risk of reduction climate change need be cut and be deposited CO ₂

Summary of the invention

In some embodiments, the invention provides a kind of method, described method comprises the solution of a) self-contained divalent cation and comprises CO ₂Industrial gaseous waste produce synthetic CARBONATE COMPONENT and b) in the concrete composition (reduced-carbon footprint concretecomposition) that the carbon footprint reduces, introduce described synthetic CARBONATE COMPONENT, the concrete composition of wherein said carbon footprint minimizing has the carbon footprint (reduced-carbon footprint) of minimizing with respect to the normal concrete composition.In some embodiments, the concrete composition of described carbon footprint minimizing lacks than the carbon footprint of normal concrete composition.In some embodiments, the carbon footprint that has of the concrete composition that reduces of described carbon footprint is lower than 75% of normal concrete composition.In some embodiments, the carbon footprint of the concrete composition of described carbon footprint minimizing is lower than 50% of normal concrete composition.In some embodiments, the carbon footprint of the concrete composition of described carbon footprint minimizing is lower than 25% of normal concrete composition.In some embodiments, the concrete composition of described carbon footprint minimizing has carbon neutral footprint (neutralcarbon footprint).In some embodiments, the concrete composition of described carbon footprint minimizing has negative carbon footprint (negative carbon footprint).In some embodiments, the minimizing of the carbon footprint of the concrete composition that reduces of described carbon footprint is that carbonic acid gas is cut and deposits the result who is avoided with carbonic acid gas.In some embodiments, described negative carbon footprint is lower than 0 pound of CO ₂/ yd ³The concrete composition that the carbon footprint reduces.In some embodiments, described negative carbon footprint is lower than 250 pounds of CO ₂/ yd ³The concrete composition that the carbon footprint reduces.In some embodiments, described negative carbon footprint is lower than 500 pounds of CO ₂/ yd ³The concrete composition that the carbon footprint reduces.In some embodiments, described negative carbon footprint is lower than 1000 pounds of CO ₂/ yd ³The concrete composition that the carbon footprint reduces.In some embodiments, described synthetic CARBONATE COMPONENT is supplementary cementitious material, fine aggregate, coarse aggregate or active pozzolans material.In some embodiments, described synthetic CARBONATE COMPONENT is aragonite, nesquehonite, hydromagnesite, single hydroconite or its combination.In some embodiments, the described synthetic CARBONATE COMPONENT combination that is aragonite and hydromagnesite.In some embodiments, the described synthetic CARBONATE COMPONENT combination that is aragonite and nesquehonite.In some embodiments, the described synthetic CARBONATE COMPONENT combination that is nesquehonite and single hydroconite.In some embodiments, the δ of described synthetic CARBONATE COMPONENT ¹³C is lower than-10 ‰.In some embodiments, the δ of described synthetic CARBONATE COMPONENT ¹³C is lower than-20 ‰.In some embodiments, the δ of described synthetic CARBONATE COMPONENT ¹³C is lower than-30 ‰.

In some embodiments, the invention provides the composition that a kind of carbon footprint that produces by the method that may further comprise the steps reduces: a) solution of self-contained divalent cation and comprise CO ₂Industrial gaseous waste produce synthetic CARBONATE COMPONENT and b) in the concrete composition that the carbon footprint reduces, introduce described synthetic CARBONATE COMPONENT, the concrete composition that wherein said carbon footprint reduces has the carbon footprint of minimizing with respect to the normal concrete composition.

In some embodiments, the invention provides a kind of composition, described composition comprises the calcium of 2.5%-50%, the magnesium of 2.5%-50% and at least 25% carbonate, supercarbonate or its mixture.In some embodiments, described composition comprises the calcium of 2.5%-25%.In some embodiments, described composition comprises the calcium of 5%-10%.In some embodiments, described composition comprises the magnesium of 5%-30%.In some embodiments, described composition comprises the magnesium of 10%-30%.In some embodiments, described composition comprises at least 50% carbonate, supercarbonate or its mixture.In some embodiments, described composition comprises at least 75% carbonate, supercarbonate or its mixture.In some embodiments, described composition comprises aragonite, nesquehonite, hydromagnesite, single hydroconite or its combination.In some embodiments, described composition comprises the combination of aragonite and hydromagnesite.In some embodiments, described composition comprises the combination of aragonite and nesquehonite.In some embodiments, described composition comprises the combination of nesquehonite and single hydroconite.

In some embodiments, the invention provides a kind of CO of comprising ₂Cut the concrete composition of the carbon footprint minimizing of depositing component.Described CO ₂Cut and to deposit component and can be supplementary cementitious material or aggregate such as coarse aggregate or fine aggregate.In some embodiments, the concrete composition of described carbon footprint minimizing comprises CO ₂Cut and deposit supplementary cementitious material and CO ₂Cut and deposit aggregate.In some embodiments, the concrete composition of described carbon footprint minimizing comprises portland cement clinker.

In some embodiments, the invention provides a kind of solidifiable composition, described solidifiable composition comprises the concrete composition of water and the minimizing of carbon footprint, and the concrete composition that described carbon footprint reduces comprises CO ₂Cut and deposit component.Described CO ₂Cut and to deposit component and can be supplementary cementitious material or aggregate such as coarse aggregate or fine aggregate.In some embodiments, the concrete composition of described carbon footprint minimizing comprises CO ₂Cut and deposit supplementary cementitious material and CO ₂Cut and deposit aggregate.In some embodiments, the concrete composition of described carbon footprint minimizing comprises portland cement clinker.

In some embodiments, the invention provides the concrete method of a kind of preparation, described method comprises merging water cement and CO ₂Cut and deposit component.Described CO ₂Cut and to deposit component and can be supplementary cementitious material or aggregate such as coarse aggregate or fine aggregate.In some embodiments, the concrete composition of described carbon footprint minimizing comprises CO ₂Cut and deposit supplementary cementitious material and CO ₂Cut and deposit aggregate.In some embodiments, the concrete composition of described carbon footprint minimizing comprises portland cement clinker.

In some embodiments, the invention provides a kind of merging water and comprise CO ₂The concrete composition that cuts the carbon footprint minimizing of depositing component is to produce the aquation concrete composition and to make described aquation concrete composition be frozen into the method for solid articles.Described CO ₂Cut and to deposit component and can be supplementary cementitious material or aggregate such as coarse aggregate or fine aggregate.In some embodiments, the concrete composition of described carbon footprint minimizing comprises CO ₂Cut and deposit supplementary cementitious material and CO ₂Cut and deposit aggregate.In some embodiments, the concrete composition of described carbon footprint minimizing comprises portland cement clinker.In some embodiments, described solid articles is a structural articles.

The accompanying drawing summary

New feature of the present invention provides in subsidiary claims in detail.In conjunction with below provide the detailed description and the accompanying drawing thereof of the exemplary of wherein having used principle of the present invention, feature of the present invention and advantage will be better understood, in the accompanying drawings:

Fig. 1 has provided the method for generation sedimentable matter of the present invention.

Fig. 2 shows the system of generation sedimentable matter of the present invention.

Fig. 3 has provided the intensity-fate graphic representation of a composition of the present invention.

Fig. 4 shows the preparation of sedimentable matter of the present invention and/or cement.

Fig. 5 has provided the system of generation sedimentable matter of the present invention and/or cement.

Fig. 6 shows the preparation of the power station stack gas of sedimentable matter of the present invention, cement and/or the self-contained CO2 of concrete.

Fig. 7 has provided normal portland cement (OPC), the auxiliary gelling admixture (SCMA) of aquation and comprise 20% SCMA and Fourier transform infrared (FT-IR) spectrogram of aquation mixture in the time of 7 days of 80% OPC not.

Fig. 8 has provided OPC and has comprised 20% SCMA and the x-ray diffraction pattern (XRD) of aquation mixture in the time of 7 days of 80% OPC.

Fig. 9 has provided aquation OPC, not aquation OPC, aquation SCMA and comprise 20% SCMA and the x-ray diffraction pattern (XRD) of the aquation mixture of 80% OPC not.

Figure 10 has provided aquation OPC and has comprised 20% SCMA and scanning electronic microscope (SEM) image of the aquation mixture of 80% OPC.

Figure 11 shows that SCMA of the present invention is active.

Figure 12 has provided the different shape of supplementary cementitious material of the present invention.

Detailed Description Of The Invention

In some embodiments, the invention provides the concrete composition that the carbon footprint reduces. The concrete that carbon footprint of the present invention reduces have comprise carbonate, bicarbonate or its combination component (such as CO₂Cut and deposit component). Other aspects of the present invention comprise preparation and the concrete method of using described carbon footprint to reduce.

Before describing the present invention in more detail, should understand and the invention is not restricted to described particular herein, because such embodiment is variable. Should also be understood that the term used is only for the purpose of describing particular but not be intended to restriction herein. Scope of the present invention is only limited by subsidiary claims. All technology and the scientific terminology of using herein has the common identical implication of understanding such as those skilled in the art of the invention, except other points out.

In the situation of the scope that has provided value, should understand, each insertion value between the bound of this scope (unless spell out in addition, otherwise to described lower limit unit 1/10th) and this specified scope in any other appointment or insertion value all be encompassed in the present invention. These bounds more among a small circle can be included in independently described more among a small circle in and also be encompassed in the present invention, in the scope of appointment except any limit of clearly getting rid of. When the scope of appointment comprises in two limit one or two, get rid of arbitrary in those included limit or the scope of the two is also included among the present invention.

Some scope that provides herein is preced with term " about " before numerical value. Term " about " is used for approaching or approximate number provides the literal support for thereafter definite number and with number behind this term in this article. When determining whether a number approaches or be similar to the severals that certain clearly puts down in writing, approaching the or approximate number of record not can be and provides in the context of its appearance and the described number that is equal in fact of clearly putting down in writing number.

The open case of all that quote in this specification, patent and patent application case are with incorporated herein by reference as the degree that every part of independent open case, patent or patent application case specifically and is individually pointed out to incorporate into by reference. In addition, the open case of every portion of quoting, patent or patent application case are incorporated herein by reference with the disclosure and description theme relevant with the open case of being quoted. Any open case quote for be that the present invention submits a few days ago open to but should not be construed as and admits that the present invention haves no right according to formerly inventing prior to the open case of this class. In addition, the given open date may be different from the open date of reality, and the actual open date may need independent affirmation.

Should point out, reach singulative " ", " a kind of " and " being somebody's turn to do " of using in subsidiary claims herein and comprise that plural number refers to, except spelling out in addition in the context. Be also pointed out that claims can draft to getting rid of any optional key element. Therefore, this statement is intended to use and uses the exclusiveness term such as the preposition basis of " only ", " only " etc. or use " negating " restrictive condition when being described herein the claim key element.

It is evident that for those skilled in the art after reading the disclosure, herein described and shown in each indivedual embodiment have discrete part and feature, described feature can be easy to separate with the feature of any other some embodiments or make up and not depart from scope of the present invention or spirit. Any method of putting down in writing all can be carried out in proper order by the event sequence of putting down in writing or by possible any other in logic. To be described representational illustrative methods and material below, but also can be used and described those any method and materials similar or of equal value herein in enforcement of the present invention or the test.

Further describing when of the present invention, will describe concrete composition that the carbon footprint reduces and preparation method thereof and system at first in more detail.Then will further summarize the method afford that uses the concrete composition that described carbon footprint reduces.The concrete composition that the carbon footprint reduces

In some embodiments, the invention provides the concrete composition that the carbon footprint reduces.The concrete composition that the carbon footprint reduces for containing normal portland cement (OPC) component for example but with only contain OPC for example compares the carbon footprint with minimizing as the concrete of cement component concrete composition.In some embodiments, the concrete composition of described carbon footprint minimizing comprises the carbon that is derived from the human fuel (as fossil oil) that uses.For example, the concrete composition that reduces of carbon footprint according to aspects of the present invention comprises from the burning of fossil oil and with CO ₂The carbon that form discharges.In certain embodiments, cut the carbon of depositing in the composition of the present invention (as the concrete composition of carbon footprint minimizing) and comprise carbonate, supercarbonate or its mixture.Therefore, in certain embodiments, the concrete composition carbonate containing that according to aspects of the present invention carbon footprint reduces can be derived from the human fuel (as fossil oil) that uses to small part carbon in the wherein said carbonate.Therefore, the preparation of the concrete composition of carbon footprint minimizing of the present invention will make CO ₂Place to can be used as for example form of the shelf-stable of the integral part of architectural environment, described environment comprises man-made structures such as buildings, wall, road etc.Therefore, the preparation of the concrete composition of carbon footprint minimizing of the present invention will prevent CO ₂Gas enters atmosphere.

About the calculating of carbon footprint, concrete carbon footprint can be by taking advantage of its every pound carbon footprint number, these value summations being added 10.560kg/yd again with every cubic yard of poundage of each constituent element ³(1 yard concrete transports 20 miles average carbon footprint) calculates.About the OPC component, suppose the average CO that produces from portland cement ₂Burst size is 0.86 tonne of CO ₂/ metric ton cement (according to California Cement Climate Action Team's), then the carbon footprint of the production of every pound of portland cement is 0.86 pound.The assumed average shipment distance is 100 miles, and the transportation footprint of every pound of portland cement is 0.016 pound, so the total carbon footprint of every pound of OPC is 0.876 pound of CO ₂With regard to carbon footprint computation purpose, the carbon footprint of conventional aggregate can be assumed to 0.043 pound of CO ₂/ pound aggregate, and conventional supplementary cementitious material (SCMs) can be assumed to 0.045 pound of CO as the carbon footprint of flyash, slag etc. ₂The conventional SCM of/pound.Compare as the normal concrete of unique cement component with OPC with comprising conventional aggregate (as sand and/or rock), the carbon footprint of the concrete composition that carbon footprint of the present invention reduces reduces amplitude can be equal to or higher than 25 pounds of CO ₂/ yd ³Concrete, 50 pounds of CO ₂/ yd ³Concrete, 100 pounds of CO ₂/ yd ³Concrete, be higher than 200 pounds of CO ₂/ yd ³Concrete, be higher than 300 pounds of CO ₂/ yd ³Concrete, be higher than 400 pounds of CO ₂/ yd ³Concrete or be higher than 500 pounds of CO ₂/ yd ³Concrete.For example, comprise OPC, 20% CO ₂The carbon footprint reduction of concrete composition of cutting the carbon footprint minimizing of the flyash deposit SCM (SCM that for example comprises carbonate, supercarbonate or its combination) and 20% can be about 250 pounds of CO ₂/ yd ³Concrete, for example reduction is 244 pounds of CO ₂/ yd ³Concrete.The carbon footprint of the concrete composition that such carbon footprint reduces is almost half of charcoal footprint of conventional concrete composition.

These of carbon footprint reduce available concrete mixture and obtain, and described compound contains the conventional SCMs that is lower than 50% weight, for example is lower than the conventional SCMs of 40% weight, comprises the conventional SCMs that is lower than 30% weight, for example is lower than 20% SCMs.Term " water cement " uses with its conventional meaning, refer to water or wherein solvent be that the solution (as admixture solution) of water merges after coagulation and hardened composition.Merge cement of the present invention and the liquid, aqueous product that produces to solidify and harden be the result who produces hydrate, described hydrate forms when being reacted with water by cement, wherein said hydrate is water insoluble substantially.

In certain embodiments, the concrete composition that carbon footprint of the present invention reduces is neutral carbon (carbon neutral), does not have (if any) carbon footprint substantially because use-case such as the calculation criterion that provides are above calculated it.Neutral carbon concrete composition of the present invention comprises that the carbon footprint is lower than 50 pounds of CO ₂/ yd ³Concrete, for example be lower than 25 pounds of CO ₂/ yd ³Concrete, comprise and be lower than 10 pounds of CO ₂/ yd ³Concrete, for example be lower than 5 pounds of CO ₂/ yd ³Concrete those compositions.In some embodiments, the carbon footprint that has of neutral carbon concrete composition is 0 pound of CO ₂/ yd ³Concrete or lower for example has and is lower than (promptly more being defeated by)-1 pound CO ₂/ yd ³Concrete, be lower than-2 pounds of CO ₂/ yd ³Concrete, be lower than-3 pounds of CO ₂/ yd ³Concrete, be lower than-4 pounds of CO ₂/ yd ³Concrete or be lower than-5 pounds of CO ₂/ yd ³Concrete negative carbon footprint.For example, comprise OPC and mainly be that synthetic fine aggregate (is CO ₂Cut and to deposit aggregate, it comprises carbonate, supercarbonate or its mixture) the carbon footprint reduction of concrete composition can be higher than 500 pounds of CO ₂/ yd ³Concrete (537 pounds of CO for example ₂/ yd ³Concrete) thus described concrete composition can be regarded as neutral carbon.Can by replace (also claiming " avoiding ") for example part of O PC make such neutral carbon concrete composition have more negative carbon footprint.For example, comprise 60% OPC, 20% flyash, 20% CO ₂Cut and to deposit SCM (SCM that for example comprises carbonate, supercarbonate or its mixture) and parts of fine aggregate to be synthesized fine aggregate (be CO ₂Cut and to deposit aggregate, it comprises carbonate, supercarbonate or its mixture) institute's alternate concrete composition can have neutral carbon footprint or quite negative carbon footprint.

In some embodiments, as mentioned above, low-carbon (LC) footprint concrete has quite negative carbon footprint.In such embodiments, the negative carbon footprint of composition can be lower than (promptly more being defeated by)-10 ,-25 ,-50 ,-100 ,-250 ,-500 ,-750 or-1000 pounds of CO ₂/ yd ³Concrete.For example, comprise OPC, 20% CO ₂Cut and to deposit SCM (SCM that for example comprises carbonate, supercarbonate or its mixture), 100% synthetic fine aggregate (is that unique synthetic fine aggregate is CO ₂Cut and to deposit fine aggregate, it comprises carbonate, supercarbonate or its mixture), 100% synthetic coarse aggregate (is that unique synthetic coarse aggregate is CO ₂Cut and to deposit coarse aggregate, it comprises carbonate, supercarbonate or its mixture) concrete composition can have and be lower than-1000 pounds of CO ₂/ yd ³Concrete, 1146 pounds of CO for example ₂/ yd ³Concrete quite negative carbon footprint.Such concrete composition is because thereby CO has also been avoided in replacement ₂Produce component (as OPC) and can have even higher carbon footprint reduction (promptly even more negative carbon footprint).Therefore, comprise CO ₂Cut and to deposit the component component of carbonate, supercarbonate or its mixture (as comprise) replaced C O ₂The concrete composition that produces component can have reflection CO ₂The quite negative carbon footprint of avoiding only, the carbon footprint of wherein said concrete composition can be lower than (promptly more being defeated by)-1000 pound CO ₂/ yd ³Concrete, for example-1250 pound CO ₂/ yd ³Concrete comprises-1500 pounds of CO ₂/ yd ³Concrete, for example-1750 pound CO ₂/ yd ³Concrete or lower.For example, comprise OPC, 20% CO ₂Cut and to deposit the SCM SCM of carbonate, supercarbonate or its mixture (as comprise), 100% CO ₂Cutting and depositing fine aggregate (is that unique fine aggregate is CO ₂Cut and to deposit fine aggregate, it comprises carbonate, supercarbonate or its mixture), 100% CO ₂Cutting and depositing coarse aggregate (is that unique coarse aggregate is CO ₂Cut and to deposit coarse aggregate, it comprises carbonate, supercarbonate or its mixture) concrete composition because of having avoided CO only ₂And can have quite negative carbon footprint, wherein said negative carbon footprint can be for example 1683 pounds of CO ₂/ yd ³Concrete.

In some embodiments, the feature of the concrete composition of carbon footprint minimizing of the present invention can be to comprise cement component and aggregate component.Cement component contains the conventional water cement such as the OPC of certain share, and can maybe can not conform to one or more conventional SCMs such as flyash, slags etc.Aggregate component contains thin and/or coarse aggregate.The aspect of described concrete composition comprises and has CO ₂Cut and to deposit the component component of carbonate, supercarbonate or its mixture (as comprise), for example CO ₂Cut and deposit SCM and/or thin or thick CO ₂Cut and deposit aggregate.Below to each these components more detailed description in addition respectively.

The concrete composition that uses carbon footprint of the present invention to reduce can bring a large amount of results that reduce of carbon footprint.For example, unite and avoid CO ₂Cement (offsetting the use of normal portland cement) can bring the result who subtracts carbon in a large number with the amount deposit carbon from cutting of fossil point source.The carbonate component that comprises of the present invention per ton is (as CO ₂Cut and to deposit component) material can make CO ₂Minimizing for example 1.2 tons or more, comprises 1.6 tons or more, for example 2 tons or more up to 1 ton or more.The carbonate that comprises of the present invention is (as CO ₂Cut and to deposit component) mixtures such as various binary, ternary, quaternary can bring such minimizing.Described carbonate component is (as CO ₂Cut and deposit component) can for example use the mixed cement of low to produce, neutral (promptly being about zero) or negative carbon footprint with flyash, slag and/or normal portland cement as supplementary cementitious material (SCM).Such mixed cement 28 days or following, for example 14 days or following also can have be equal to or higher than 1,000psi, comprise and be equal to or higher than 2,000psi, for example be equal to or higher than 2, the ultimate compression strength of 500psi.Therefore, the mixed cement with low, neutral or negative carbon footprint of the present invention can produce and be suitable for being used in the quality concrete of concrete road surface in using.

That the concrete composition that the carbon footprint reduces comprises is low-, neutral-or the concrete composition of negative-carbon footprint.In some embodiments, low-, neutral-or the concrete composition of negative-carbon footprint comprise mixed cement (as CO ₂Cut and deposit supplementary cementitious material (SCM) together with flyash, slag and/or portland cement) and CO ₂Cut and deposit aggregate (for example described aggregate is coarse aggregate, fine aggregate such as sand etc.), described aggregate can be from carbonate component of the present invention (as CO ₂Cut and deposit component) by U.S. Patent application 12/475,378 preparation of submitting on May 29th, 2009, this patent application is attached to herein by reference.Such composition can for example contain a section CO who deposits ₂Content be about 20% or more, for example 35% or more, comprise 50% or more fine aggregate (as sand).In some embodiments, described low-, neutral-or the ultimate compression strength of concrete composition in the time of 28 days of negative-carbon footprint can be 2,500psi or higher, for example 3,000psi or higher comprises 4,000psi.Some embodiments provide the concrete composition of negative carbon footprint, and its ultimate compression strength in the time of 28 days is 4,000psi.Impartial early strength (promptly in the time of 28 days) make of the present invention low-, neutral-or the use of the concrete composition of negative-carbon footprint will can the negative impact construction speed.

In some embodiments, the invention provides low-, neutral-or the concrete composition of negative-carbon footprint, described concrete composition not only satisfies intensity and early strength standard, and final strength is as the normal concrete composition.The behavior of mixed cement-concrete composition of the present invention is similar to conventional OPC-concrete composition, and this makes the present invention can be used on similar place and plays similar function.In some embodiments, mixed cement-concrete composition can be used among the present invention.Can use mixed cement-concrete composition of the present invention in some embodiments.For example, mixed cement-concrete composition can be cast in (for example 5,000 square feet parking lot) in the parking area.Because mixed cement-concrete composition has higher albedo, so this based composition will reduce carbon emission by reducing lighting demand.This carbon emission reduction can exist in the time limit of service of mixed cement-concrete composition.For example; comprise low-, neutral-or the contrast of the albedo of the parking area of negative-carbon footprint concrete composition and brightness measuring result and asphalted parking area can be used to determine the difference of required illumination, thereby definite because of using the carbon emission reduction level possible of the present invention than the concrete composition of high albedo.The test of the albedo of this based composition show its ability that reduces urban heat land effect for example reach 2 times or more, 5 times or more, 10 times or more, 20 times or more.

Conventional water cement

A kind of component of composition of the present invention can be conventional water cement.Conventional water cement is non-CO ₂Cut any cement of the water mud cement of synthetic carbonate, synthetic supercarbonate or its mixture (as comprise), this will be described in greater detail below.The conventional water cement of being concerned about in certain embodiments is a portland cement.Described portland cement component can be any suitable portland cement.As known in the art, portland cement is the calcium sulfate by grinding portland cement clinker (surpassing 90%), limited amount setting-time control and the powder composition of 5% less important constituent element (as various standards permissions) generation at the most.By the definition of European standard EN197.1, portland cement clinker is a hydraulic material, and it should be by the Calucium Silicate powder (3CaOSiO of 2/3 quality ₂And 2CaOSiO ₂) form, all the other are formed with other compounds with ferruginous grog mutually by containing aluminium.CaO and SiO ₂Ratio should be not less than 2.0.Mg content (MgO) should be no more than 5.0% quality.In certain embodiments, portland cement constituent element of the present invention can be any portland cement that satisfies ASTM C150 (I-VIII class) standards and norms (ASTMC50-portland cement standard specifications) of American Society for testing and materials.ASTM C150 is contained eight class portland cements, and every class has different character and specifically uses according to its character.

In set concrete composition of the present invention, the amount of portland cement component can be different.In certain embodiments, the amount of portland cement is in 10-90% (w/w) scope in the mixture, and for example 30-70% (w/w) comprises 40-60% (w/w), for example 80% OPC and 20% CO of the present invention ₂Cut the mixture deposit the SCM SCM of carbonate, supercarbonate or its mixture (as comprise).

Conventional SCMs

Cement can also contain one or more auxiliary gelling composition such as flyash, slags etc.In certain embodiments, cement can be compound, because its carbonate containing compound composition component but also contain one or more and can add to improve other components of cement character, desirable strength for example to be provided, required setting time etc. is provided not only.The component of being concerned about that can exist in the mixed cement of the present invention includes but not limited to: blast-furnace slag, flyash, diatomite, natural or artificial volcanic ash, silicon ash, Wingdale, gypsum, white lime etc.The amount of this class component (if present) that exists in the set concrete composition of the present invention can be different, and in certain embodiments, the amount of these components is in the 1-50%w/w scope, and for example 2-25%w/w comprises 10-20%w/w.

CO ₂Cut and deposit component

CO of the present invention ₂Cut and to deposit the material that material (also claiming " carbon cuts and deposits material ") comprises carbonate containing and/or supercarbonate, it can make up with divalent cation such as calcium and/or magnesium or with monovalent cation such as sodium.Described carbonate and/or supercarbonate can be in solution, be solid form or be the combination (as slurry) of solution and solid form.Described carbonate and/or supercarbonate can contain the carbonic acid gas from carbon dioxide source; In some embodiments, described carbonic acid gas is derived from the burning of fossil oil, and therefore some (as at least 10,50,60,70,80,90,95%) in described carbonate and/or the supercarbonate or whole substantially (as at least 99,99.5 or 99.9%) carbon are fossil fuel source (being plant-sourced).FOR ALL WE KNOW, the carbon of the carbon of plant-sourced and inorganic sources have different stable isotopes ( ¹³C and ¹²C) ratio, therefore in some embodiments, the δ of the carbon in described carbonate and/or the supercarbonate ¹³The C value for example is lower than-10 ‰ or be lower than-15 ‰ or be lower than-20 ‰ or be lower than-25 ‰ or be lower than-30 ‰ or be lower than-35 ‰.

Generalized as top institute, CO ₂Cut and to deposit component and not only comprise supplementary cementitious material but also comprise thin and thick aggregate, wherein CO ₂Cut and to deposit component and stably store a large amount of CO with the form of carbonate, supercarbonate or its mixture ₂Concrete composition carbonate containing/supercarbonate component that carbon footprint of the present invention reduces is (as CO ₂Cut and deposit component).Such component will be stored a large amount of CO with the form of shelf-stable ₂, cause CO ₂Gas can not be easily produces and discharges into the atmosphere from goods.In certain embodiments, for the concrete composition that per 1000 tons of carbon footprints of the present invention reduce, described carbonate component is (as CO ₂Cut and deposit component) can store 50 tons or more CO ₂, for example 100 tons or more CO ₂, comprise 250 tons or more CO ₂, for example 500 tons or more CO ₂, for example 750 tons or more CO ₂, comprise 900 tons or more CO ₂In certain embodiments, the carbonate component of the concrete composition of described carbon footprint minimizing is (as CO ₂Cut and to deposit component) comprise about 5% or more CO ₂, for example about 10% or more CO ₂, comprise about 25% or more CO ₂, for example about 50% or more CO ₂, for example about 75% or more CO ₂, comprise about 90% or more CO ₂(for example existing) with one or more carbonate cpdss.

Carbonate component of the present invention is (as CO ₂Cut and deposit component) can contain one or more carbonate cpdss.Use the scheme described in the coulometric titration to record by for example coulometry, described carbonate component is (as CO ₂Cut and to deposit component) in the amount of carbonate can be 40% or higher, for example 70% or higher, comprise 80% or higher.In some embodiments, when the Mg source is the ferromagnesian mineral (U.S. Patent application 12/501 that on July 10th, 2009 submitted to, the U.S. Provisional Patent Application 61/079 that on July 10th, 217 and 2008 submitted to, state in 790, it all is attached to herein by reference) or the ashes (U.S. Patent application 12/486 that on June 17th, 2009 submitted to, the U.S. Provisional Application 61/073 that on June 17th, 692 and 2008 submitted to, state in 319, it all is attached to herein by reference) time, products therefrom can be the composition that contains silicon-dioxide and carbonate.In these embodiments, the carbonate content of product can be low to moderate 10%.In in these embodiments some, the dioxide-containing silica of product can be used as cement or supplementary cementitious material provides improved performance.

The CO of the concrete composition that carbon footprint of the present invention reduces ₂Cut and to deposit the component sedimentable matter of carbonate, supercarbonate or its mixture (as comprise) long storage CO in a certain way is provided ₂, cause CO ₂Cut and deposited (promptly fixing) in the concrete composition that the carbon footprint reduces, wherein cut the CO that deposits ₂Do not become an atmospheric part.The concrete composition that reduces when the carbon footprint remains on following time of condition conventional for its desired use, and the concrete composition that the carbon footprint reduces will make the CO that deposits that cuts ₂Be maintained fixed reach the long period (for example 1 year or more of a specified duration, 5 years or more of a specified duration, 10 years or more of a specified duration, 25 years or more of a specified duration, 50 years or more of a specified duration, 100 years or more of a specified duration, 250 years or more of a specified duration, 1000 years or more of a specified duration, 10,000 year or more of a specified duration, 1,000,000 year or more of a specified duration or even 100,000,000 year or more of a specified duration), and do not have the CO of significant quantity (if any) ₂From the concrete composition that described carbon footprint reduces, discharge.The concrete composition that reduces about described carbon footprint is when being used for its desired use, in the time limit of service of the concrete composition that described carbon footprint reduces, as with CO ₂Gas release measures, and the amount of degraded (if any) will be no more than for 5% every year, will be no more than for 1% every year in certain embodiments.In fact, the concrete composition that carbon footprint provided by the invention reduces is when the condition that is exposed to normal temperature and humidity for its desired use (comprising the rainfall of normal pH) following time, will or surpass 20 years at least 1 year, 2 years, 5 years, 10 years or 20 years, for example not discharge above its total CO above in the time in 100 years ₂1%, 5% or 10%.In some embodiments, the concrete composition that the carbon footprint reduces does not discharge in the time at least 1 year above its total CO when being exposed to for its desired use normal temperature and humidity condition (comprising the rainfall of normal pH) following time ₂1%.In some embodiments, the concrete composition that the carbon footprint reduces does not discharge in the time at least 1 year above its total CO when being exposed to for its desired use normal temperature and humidity condition (comprising the rainfall of normal pH) following time ₂5%.In some embodiments, the concrete composition that the carbon footprint reduces does not discharge in the time at least 1 year above its total CO when being exposed to for its desired use normal temperature and humidity condition (comprising the rainfall of normal pH) following time ₂10%.In some embodiments, the concrete composition that the carbon footprint reduces does not discharge in the time at least 10 years above its total CO when being exposed to for its desired use normal temperature and humidity condition (comprising the rainfall of normal pH) following time ₂1%.In some embodiments, the concrete composition that the carbon footprint reduces does not discharge in the time at least 100 years above its total CO when being exposed to for its desired use normal temperature and humidity condition (comprising the rainfall of normal pH) following time ₂1%.In some embodiments, the concrete composition that the carbon footprint reduces does not discharge in the time at least 1000 years above its total CO when being exposed to for its desired use normal temperature and humidity condition (comprising the rainfall of normal pH) following time ₂1%.

Can use any suitable the surrogate markers thing or the test of this class stability of energy reasonable prediction.For example, relate to hot conditions and/or in the accelerated test of by the time more extreme pH condition can reasonably indicate stability in long-time.For example, the environment and the desired use of the concrete composition that reduces according to the carbon footprint, the sample of composition can be exposed to 50,75,90,100,120 or 150 ℃ temperature and 10% to 50% relative humidity and assign 1,2,5,25,50,100,200 or 500 day, its carbon loss is lower than 1%, 2%, 3%, 4%, 5%, 10%, 20%, 30% or 50% can think concrete composition stable ample evidence in given time (as 1,10,100,1000 or above 1000 years) that carbon footprint of the present invention reduces.

The CO of the concrete composition that the carbon footprint reduces ₂Cut the CO deposit the component sedimentable matter of carbonate, supercarbonate or its mixture (as comprise) ₂Content can be monitored by any suitable method (for example coulometry).Other conditions (comprising pH, pressure, UV radiation etc.) can suitably be adjusted according to expection or possible environment equally.Should be understood that those skilled in the art can reasonably conclude will show that composition has required stability in the specified time period any suitable condition all can use.In addition, if the chemical knowledge of generally acknowledging shows that composition will have required stability in the specified time period, then it also can be used as replenishing or substituting of practical measurement.For example, some carbonate cpdss (for example being set polycrystalline form) that can be the part of the concrete composition that carbon footprint of the present invention reduces can be know on the geology and can knownly be subjected to many decades, hundreds of years or even the normal meteorological conditions in thousands of years and do not have appreciable decomposition and therefore have required stability.

CO ₂Cut concrete composition that the amount deposit the component sedimentable matter of carbonate, supercarbonate or its mixture (as comprise) can reduce with concrete carbon footprint and different.Sometimes, CO in the concrete composition of carbon footprint minimizing ₂Cut deposit the component sedimentable matter of carbonate, supercarbonate or its mixture (as comprise) amount in 5-100% (w/w) scope, for example 5-90% (w/w) comprises 5-75% (w/w), 5-50% (w/w), 5-25% (w/w) and 5-10% (w/w).

With lack the carbonate component (as CO ₂Cut and to deposit component) corresponding concrete composition compare, the concrete composition that the carbon footprint reduces has the carbon footprint of minimizing.Use any footprint of carbon easily counter as can be known, concrete composition that carbon footprint of the present invention reduces and shortage carbonate component are (as CO ₂Cut and to deposit component) corresponding concrete composition compare the amplitude that the carbon footprint reduces and can be 5% or more, for example 10% or more, comprise 25%, 50%, 75% or even 100% or more.In certain embodiments, the concrete composition that carbon footprint of the present invention reduces can be a neutral carbon, does not have (if any) carbon footprint substantially because calculate it with any suitable carbon footprint counter that for example may be relevant with the specific concrete composition of being concerned about.The concrete composition of neutral carbon of the present invention comprises that the carbon footprint is 50 pounds of CO ₂/ yd ³Material or still less, for example be 10 pounds of CO ₂/ yd ³Material or still less, comprise 5 pounds of CO ₂/ yd ³Material or those compositions still less, wherein in certain embodiments, it is zero or negative CO that the concrete composition of neutral carbon has ₂Poundage/yd ³Material, for example negative 1 or more negative, as negative 3 or more negative CO ₂Poundage/yd ³Concrete composition.Sometimes, the concrete composition that described carbon footprint reduces has quite negative carbon footprint, for example-100 or more negative pound CO ₂/ yd ³Concrete or still less.

CO of the present invention ₂Cut and to deposit the component sedimentable matter of carbonate, supercarbonate or its combination (as comprise) and comprise the CO that has been discharged into originally in the atmosphere ₂, described CO ₂In great majority produce by the fossil oil of burning plant-sourced.Therefore, of the present inventionly comprise one or more and be derived from industrial CO ₂Carbonate synthesis salt and/or the CO of supercarbonate ₂Cut and to deposit component and will reflect described industrial CO ₂Relative carbon isotope composition (the δ of the fossil oil (as coal, oil, Sweet natural gas or flue gas) that (from the burning of fossil oil) is derived from ¹³C).Unit is the relative carbon isotope composition (δ of ‰ (thousandth) ¹³C) value is that two kinds of stable isotopes of carbon are ¹²C and ¹³The concentration rate of C is measured with respect to fossilisation belemnite standard (PDB standard).

δ ¹³C ‰=[( ¹³C/ ¹²C _Sample- ¹³C/ ¹²C _{The PDB standard})/( ¹³C/ ¹²C _{The PDB standard})] x1000

Therefore, contain the sedimentable matter of carbonate synthesis salt and/or supercarbonate (as CO ₂Cut and to deposit component) δ ¹³The C value can be served as CO ₂The CO that the fossil oil of gas source, especially auto-combustion discharges ₂Fingerprint.Different source (being fossil fuel source) can have different δ ¹³The C value, but carbonate of the present invention and/or supercarbonate component are (as CO ₂Cut and to deposit component) δ ¹³The C value is common but non-one fix in-9 ‰ to-35 ‰ scopes.In some embodiments, the δ that contains the sedimentable matter of carbonate synthesis salt ¹³The C value can be between-1 ‰ to-50 ‰, between-5 ‰ to-40 ‰, between-5 ‰ to-35 ‰, between-7 ‰ to-40 ‰, between-7 ‰ to-35 ‰, between-9 ‰ to-40 ‰ or between-9 ‰ to-35 ‰.In some embodiments, the δ that contains the sedimentable matter of carbonate synthesis salt ¹³C （）-3‰、-5‰、-6‰、-7‰、-8‰、-9‰、-10‰、-11‰、-12‰、-13‰、-14‰、-15‰、-16‰、-17‰、-18‰、-19‰、-20‰、-21‰、-22‰、-23‰、-24‰、-25‰、-26‰、-27‰、-28‰、-29‰、-30‰、-31‰、-32‰、-33‰、-34‰、-35‰、-36‰、-37‰、-38‰、-39‰、-40‰、-41‰、-42‰、-43‰、-44‰、-45‰，δ。¹³The C value is negative more, contains in the sedimentable matter of carbonate synthesis salt to be rich in more ¹²C.Can adopt any suitable method to measure δ ¹³C value, these methods include but not limited to mass spectroscopy or from axle integration chamber output spectrum method (from axle ICOS).

In some embodiments, the invention provides a kind of CO of containing ₂Cut the concrete composition of the carbon footprint minimizing of depositing component, described CO ₂Cut and to deposit component and comprise carbonate, supercarbonate or its combination, the δ of the carbon in wherein said carbonate and/or the supercarbonate ¹³The C value is lower than-5 ‰.In some embodiments, the δ of the concrete composition of described carbon footprint minimizing ¹³The C value can be between-1 ‰ to-50 ‰, between-5 ‰ to-40 ‰, between-5 ‰ to-35 ‰, between-7 ‰ to-40 ‰, between-7 ‰ to-35 ‰, between-9 ‰ to-40 ‰ or between-9 ‰ to-35 ‰.In some embodiments, the δ of the concrete composition of described carbon footprint minimizing ¹³C （）-3‰、-5‰、-6‰、-7‰、-8‰、-9‰、-10‰、-11‰、-12‰、-13‰、-14‰、-15‰、-16‰、-17‰、-18‰、-19‰、-20‰、-21‰、-22‰、-23‰、-24‰、-25‰、-26‰、-27‰、-28‰、-29‰、-30‰、-31‰、-32‰、-33‰、-34‰、-35‰、-36‰、-37‰、-38‰、-39‰、-40‰、-41‰、-42‰、-43‰、-44‰、-45‰，δ。¹³The C value is negative more, contains in the composition of carbonate synthesis salt to be rich in more ¹²C.

CO ₂Cut the carbonate cpds of depositing component and can be from divalent cation solution such as the sedimentary metastable carbonate cpds of salt water, this will be described in greater detail below.Carbonate cpds composition of the present invention contains sedimentary crystallization and/or decolorizing carbon phosphate compounds.The concrete carbonate minerals of being concerned about includes but not limited to: calcium carbonate mineral, magnesiumcarbonate mineral and miemite mineral.The calcium carbonate mineral of being concerned about includes but not limited to: calcite (CaCO ₃), aragonite (CaCO ₃), veterite (C _aCO ₃), six water carbide (CaCO ₃6H ₂O) and amorphous calcium carbonate (CaCO ₃NH ₂O).The magnesiumcarbonate mineral of being concerned about include but not limited to: magnesite (MgCO ₃), hydromagnesite (MgCO ₃2H ₂O), nesquehonite (MgCO ₃3H ₂O), five hydromagnesite (MgCO ₃5H ₂O) and amorphous carbonic acid magnesium calcium (MgCO ₃NH ₂O).The miemite mineral of being concerned about include but not limited to rhombspar (CaMgCO ₃), huntite (CaMg ₃(CO ₃) ₄) and water huntite (Ca ₂Mg ₁₁(CO ₃) ₁₃H ₂O).In certain embodiments, noncarbonate compound such as brucite (Mg (OH) ₂) also can form with the mineral assemblage ground of listing above.As top pointed, the compound of described carbonate cpds composition can be metastable carbonate cpds more stable in salt water than in fresh water (and can contain one or more metastable oxyhydroxide), to such an extent as to it dissolves when contacting with the fresh water of any pH and redeposition becomes stable compound of other fresh water such as mineral as low Mg calcite.

Carbonate component of the present invention is (as CO ₂Cut and to deposit component) can be derived from, for example precipitable from divalent cation solution (for example aqueous solution of divalent cation) (this will be described in greater detail below).Because described carbonate component is (as CO ₂Cut and deposit component) can be from water precipitation, so it may contain one or more components that exist in its water that is derived from.For example, when described divalent cation solution is salt water, CO ₂Cut and to deposit the goods sedimentable matter of carbonate, supercarbonate or its mixture (as comprise) and will contain one or more compounds that exist in the salt water source.These compounds can identify (identify) solid precipitation from the composition in salt water source, and wherein these sign components and amount thereof can be referred to as salt water source marker in this article.For example, if the salt water source is a seawater, then the mark compounds that may exist in the sedimentable matter includes but not limited to: muriate, sodium, sulphur, potassium, bromide, silicon, strontium etc.Any this class source sign or " mark " element are usually to exist in a small amount, and for example with 20,000ppm or amount still less exist, for example 2000ppm or amount still less.In certain embodiments, " mark " compound can be strontium, and it for example can be incorporated in the aragonite lattice and account for 10,000ppm or still less, in certain embodiments at 3-10, in the 000ppm scope, 5-5000ppm for example, comprise 5-1000ppm, for example 5-500ppm comprises 5-100ppm.Another that be concerned about " mark " compound is a magnesium, its can be at the most 20% mole measure for the calcium in the carbonate cpds and exist.The salt water source marker of composition can be different with the concrete salt water source that is used for preparing the carbonate salt composition that is derived from salt water.What also be concerned about is the isotope tag thing at sign water source.

In certain embodiments, the CO that comprises carbonate, supercarbonate or its mixture ₂Cut and to deposit component and can be supplementary cementitious material.Though SCMs for himself can be or can not be the hydraulic gelling will be to a certain extent produce those materials of hardened material with hydraulic cement compositions such as portland cement reaction.In certain embodiments, CO ₂Cut and to deposit the SCMs SCM of carbonate, supercarbonate or its mixture (as comprise) and can be SCM per ton and store about 0.5 ton or more CO ₂, for example about 1 ton or more CO ₂, comprise about 1.2 tons or more CO ₂For example, CO of the present invention ₂Cut and to deposit the SCM SCM of carbonate, supercarbonate or its mixture (as comprise) and can store about 0.5 ton or more CO ₂SCM material per ton.In other words, CO of the present invention ₂Cut and to deposit the SCM SCM of carbonate, supercarbonate or its mixture (as comprise) and can have and be-0.5 ton of CO ₂The negative carbon footprint of material per ton.In these embodiments, CO ₂Cut and to deposit that compound (as carbonate, supercarbonate or its combination) can be done particulate composition such as powder exists.In certain embodiments, described dried particulate composition can by as record the particle formation that median size is 0.1-100 micron, for example 10-40 micron with any suitable particle size determination method such as multi-detector laser light scattering or screening (promptly＜38 micron).There are multimodal such as bimodal or other distributions in certain embodiments.Bimodal distribution can make surface-area minimize, thereby Gu and allows the lower liquid/mass ratio of cement also to provide less reactive particle to be used for early response.In these cases, the median size of greater particle size grade can surpass 1000 microns (1mm).The surface-area that constitutes the component of SCM can be different.The average surface area of set cement is enough to provide the liquid-solid ratio that produces solidifiable composition (for example being described in more detail below) when with liquid combination, and described average surface area is at 0.5m ²/ gm is to 50m ²In/gm the scope, 0.75-20m for example ²/ gm comprises 0.80-10m ²/ gm.In certain embodiments, as use Breunner, the described surface area test method of Emmit and Teller (1953) records, and the surface-area of cement is at 0.9-5m ²In/gm the scope, for example 0.95-2m2/gm comprises 1-2m ²/ gm.

When existing, CO in the concrete composition ₂Cutting the amount deposit the SCM SCM of carbonate, supercarbonate or its mixture (as comprise) can be different.In certain embodiments, concrete contains 5-50%w/w, for example 5-25%w/w, comprises 5-10%w/w, comprises the CO of 10%-25%w/w ₂Cut and to deposit the SCM SCM of carbonate, supercarbonate or its mixture (as comprise).In certain embodiments, surpassing 50% in the cement is the carbonate cpds composition.

Replaced C O ₂Cut and deposit SCM or remove CO ₂Cut and deposit outside the SCM, concrete composition can contain the CO of one or more types ₂Cut and to deposit the aggregate aggregate of carbonate, supercarbonate or its mixture (as comprise), described aggregate can be fine aggregate, coarse aggregate etc.The term aggregate uses in mode that it is generally acknowledged in this article, refers to can be used on concrete, mortar and for example microparticle compositions in the other materials as defined above.Aggregate of the present invention can be microparticle compositions, and it can be divided into fine aggregate and coarse aggregate.Fine aggregate according to embodiment of the present invention is the microparticle compositions that almost completely passes through No. 4 sieves (ASTM C 125 and ASTM C 33).In 0.001 inch to 0.25 inch scope, for example 0.05 inch to 0.125 inch, comprise 0.01 inch to 0.08 inch according to the median size of the fine aggregate composition (it can be described as " sand ") of embodiment of the present invention.Therefore, the surrogate of fine aggregate useful as concrete composition medium sand.Coarse aggregate of the present invention is for mainly being trapped in the composition on No. 4 sieves (ASTM C 125 and ASTM C 33).According to the coarse aggregate composition of embodiment of the present invention be median size 0.125 inch to 6 inches, for example 0.187 inch to 3.0 inches, comprise 0.25 inch to 1.0 inches composition.Therefore, the surrogate of conventional aggregate in the coarse aggregate useful as concrete composition.

In some embodiments, CO of the present invention ₂Cut and to deposit aggregate (the synthetic aggregate that promptly comprises carbonate, supercarbonate or its mixture) and can be aggregate storing per ton about 0.5 ton or more CO ₂, for example about 1 ton or more CO ₂, comprise about 1.2 tons or more CO ₂For example, CO of the present invention ₂Cut and to deposit the aggregate aggregate of carbonate, supercarbonate or its mixture (as comprise) and can store about 0.5 ton or more CO ₂Material per ton.In other words, CO of the present invention ₂Cut and to deposit the aggregate aggregate of carbonate, supercarbonate or its mixture (as comprise) and can have and be-0.5 ton of CO ₂The negative carbon footprint of material per ton.In addition, the density of aggregate of the present invention can be different, as long as aggregate can provide required character for the material of construction that wherein adopts described aggregate.In some cases, the density of aggregate is in the 1.1-5gm/cc scope, and for example 1.5gm/cc comprises that to 3.15gm/cc 1.8gm/cc is to 2.7gm/cc.The hardness that constitutes the particles of aggregates of aggregate composition of the present invention also can be different, and in some cases, Mohs' hardness is in the 1.5-9 scope, and for example 2-7 comprises 4-5.

The weight ratio of cement component (for example grog and SCM) and aggregate component (for example thin and coarse aggregate) can be different.In certain embodiments, the weight ratio of cement component and aggregate component is 1 in the dry concrete component: 10-4: in 10 scopes, and for example 2: 10-5: 10, comprise 55: 1000-70: 100.

The CO that comprises carbonate, supercarbonate or its mixture of the present invention ₂Cut and to deposit aggregate and contain one or more and for example reach the carbonate cpds that in U.S. Provisional Application 61/056,972, further describes as mentioned above.

Admixture

In certain embodiments, cement can use with one or more admixtures.In some embodiments, cement can with one or more CO ₂Cut and to deposit admixture and use together.Admixture is to be added in the concrete so that it has the desired characteristic that can not obtain with the base concrete mixture or makes it be easier to use or be more suitable for specific purpose or the composition to reduce cost to change concrete character.As known in the art, admixture can be any material or the composition except that water cement, aggregate and water, and its component as concrete or mortar is used to strengthen its some characteristics or to reduce its cost.The amount of the admixture that adopts can be different with the character of admixture.In certain embodiments, the amount that comprises these components of synthesizing admixture is in the 1-50%w/w scope, and for example 5-25%w/w comprises 10-20%w/w, for example 2-10%w/w.

Use the major cause of admixture to can be (1) in the gained maturing, to obtain some texture improvement; (2) to improve whole mixing during unfavourable weather or the traffic conditions, to transport, build the successive stage quality of concrete with maintenance; (3) to overcome some emergency situation in the concrete placement operating process; And/or (4) are to reduce the cost of concrete structure.Sometimes, required concrete performance feature only can obtain by using admixture.Sometimes, use admixture to make it possible to use cheaper construction process of price or design, its saving amount can remain after balancing out the cost of admixture in addition.

The admixture of being concerned about comprises mineral additive in small, broken bits.Mineral additive in small, broken bits is the material of powder or pulverised form, is added to before mixing process or in the process in the concrete to improve or the plasticity of change portland cement concrete or some in the hardening.Mineral additive in small, broken bits can be categorized as by its chemistry or physical properties: gelling material; Volcanic ash; Volcano grey matter gelling material; With the nominal inert material.Volcanic ash is siliceous or the alumina-silica material, has the gelling value hardly or not, but will form the material with gelling with the calcium hydroxide generation chemical reaction that aquation discharged of portland cement when being form in small, broken bits and having water to exist.Volcanic ash also can be used to reduce under the pressure water migration by concrete speed.Diatomite, opal matter flint (opaline cherts), clay, shale, flyash, silicon ash, volcanic tuff and float stone are some volcanic ash of knowing.Some levigate granulated blast-furnace slag and high-calcium fly ass have volcanic ash character and gelating property simultaneously.The nominal inert material also can comprise unprocessed quartz in small, broken bits, rhombspar, Wingdale, marble, grouan etc.Flyash defines in ASTM C618.

The material (as wollastonite, mafite such as peridotites and serpentine) that can use flyash and comprise metal silicate produces CO ₂Cut and deposit pozzolanic materials (promptly synthetic admixture), described CO ₂Cut and to deposit pozzolanic materials and can be used in neutral carbon of the present invention or the carbon negativity concrete composition.State in U.S. Patent application 12/486,692 that this class pozzolanic materials was submitted on June 17th, 2009 and the U.S. Patent application of submitting on July 10th, 2,009 12/501,217, its each be attached to herein by reference.In brief, except that divalent cation, proton remover or its combination, flyash (for example by slaking) or comprise metal silicate material clear up the material that also produces based on silicon-dioxide, if exist in the precipitation process of carbonate salt composition based on the material of silicon-dioxide then may be coated by lime carbonate, magnesiumcarbonate or its combination.The sedimentary nucleation site of therefore, serving as lime carbonate, magnesiumcarbonate or its mixture based on the material of silicon-dioxide.Zhi Bei pozzolanic materials can be passivated by this way, and passivation will reduce the reactivity of pozzolanic materials, and this may need in certain embodiments.The CO that comprises carbonate synthesis salt, supercarbonate or its mixture in neutral carbon or the carbon negativity concrete ₂Cut deposit pozzolanic materials can be in the 1-50%w/w scope, for example 5-25%w/w comprises 10-20%w/w, for example 2-10%w/w.In addition, CO ₂Cut deposit pozzolanic materials (as comprising the pozzolanic materials of carbonate, supercarbonate or its combination) for pozzolanic materials, its 0.25 ton of storage per ton or more CO ₂, for example 0.5 ton or more CO ₂, comprise 1 ton or more CO ₂, for example 2 tons or more CO ₂Pozzolanic materials per ton.For example, CO of the present invention ₂Cut and to deposit the pozzolanic materials pozzolanic materials of carbonate, supercarbonate or its combination (as comprise) and can store about 0.25 ton or more CO ₂Pozzolanic materials per ton.In other words, CO of the present invention ₂Cut and to deposit pozzolanic materials and can have and be-0.25 ton of CO ₂The negative carbon footprint of material per ton.

A class admixture of being concerned about can be softening agent.Softening agent can be added in the concrete so that it has improved workability, thereby is convenient to build, and reduces densification work simultaneously, and can be added in and need evenly to flow and do not stay under reinforcing bar in the Steel Concrete of void space.The admixture of being concerned about also has setting accelerator, retardant, air, pore forming material, water reducer, corrosion inhibitor and pigment.Setting accelerator is used for accelerating the hardening rate (aquation) of concrete formulation, particularly important in application that needs the concrete snap cure and lower temperature application.The effect of retardant is the hydration rate and increase deposit concrete so that it forms available time before desired shape of slowing down.Retardant concrete therein is used in particularly important in the application under the hot climate.Air is used in whole concrete the small bubble that distributes.Air is particularly useful in the zone of cold weather, because the small bubble of carrying secretly helps to allow to a certain degree pucker ﹠ bloat, thereby the protection concrete is avoided freeze-thaw damage.Also can in concrete, add pigment so that it has the required color characteristic of aesthetic purposes.

Therefore, the admixture of being concerned about includes but not limited to: setting accelerator, retardant, air, defoamer, subtract basic active agent, bonding admixture, dispersion agent, painted admixture, corrosion inhibitor, moistureproof admixture, gas forming admixture, permeability reducing agent, pumping agent, shrinkage-compensating admixture, fungicidal admixture, sterilization admixture, desinsection admixture, rheology modifier, mineral additive in small, broken bits, volcanic ash, aggregate, wetting agent, intensity reinforcing agent, water-resisting agent and any other concrete or mortar additive or additive.When using admixture, can will stir time enough so that the admixture raw material is evenly dispersed in the whole fresh concrete relatively to the cementitious composition of newly mixing of wherein having introduced the admixture raw material.

Setting accelerator is used for solidifying with early strength of accelerate concrete to be developed.Can be with the setting accelerator that the admixture system is used but be not limited to: the nitrate of basic metal, alkaline-earth metal or aluminium; The nitrite of basic metal, alkaline-earth metal or aluminium; The thiocyanate-of basic metal, alkaline-earth metal or aluminium; Alkanolamine; The thiosulphate of basic metal, alkaline-earth metal or aluminium; The oxyhydroxide of basic metal, alkaline-earth metal or aluminium; The carboxylate salt of basic metal, alkaline-earth metal or aluminium (preferable formic acid calcium); Polyhydroxy alkylamines; The halide salts of basic metal or alkaline-earth metal (as muriate).The example of available setting accelerator includes but not limited to POZZOLITH in the dispersing method of the present invention

NC534 (achloride type setting accelerator) and/or RHEOCRETE

CNI (based on the corrosion inhibitor of calcium nitrite), the two is sold with above-mentioned trade mark by joslyn hi-voltage city BASF Admixtures Inc..

The slow setting admixture of being concerned about in addition.The slow setting admixture also claims delayed setting or aquation control admixture, is used for blocking, postponing or the concrete solidification rate that slows down.It can or be added in the concrete mixture after hydration process begins when initial batching sometimes.Retardant is used for offseting the booster action of hot weather to concrete setting, or postpones that difficulty is built under the condition or the initial set of concrete or mortar when the conveying existing problems of working-yard, or sets apart for special whole operation.Most of retardant also serve as low-level water reducer and also are used for aerating in concrete.Spendable retardant includes but not limited to oxygen-boron compound, corn steep liquor, xylogen, polyphosphonic acid, carboxylic acid, hydroxycarboxylic acid, poly carboxylic acid, hydroxylation carboxylic acid (as fumaric acid, methylene-succinic acid, propanedioic acid, borax, glyconic acid and tartrate), sulfonated lignin, xitix, saccharosonic acid, sulfonic acid-acrylic copolymer and corresponding salt thereof, poly-hydroxy silane, polyacrylamide, carbohydrate and composition thereof.The illustrative example of retardant is at United States Patent (USP) 5,427, provides in 617 and 5,203,919, and described patent is attached to herein by reference.Another example that is applicable to the retardant in the admixture system of the present invention is that joslyn hi-voltage city BASF AdmixturesInc. is with trade mark DELVO

The aquation control admixture of selling.

The admixture of being concerned about also has air.The term air comprises any material with aerating in cementitious composition.Some airs also can reduce the surface tension of composition under lower concentration.The aerating admixture is used on purpose introducing the microcosmic bubble in concrete.Aerating will greatly improve the concrete weather resistance that is exposed in the freeze-thaw cycle process under the humidity.In addition, the air of carrying secretly will improve concrete greatly to the surperficial exfoliate resistivity due to the chemical deicing agent.Aerating also improves the workability of fresh concrete, eliminates simultaneously or minimizing segregation and bleeding.The material that is used for obtaining these required effects can be selected from wood resin, natural resin, synthetic resins, sulfonated lignin, petroleum acid, protein material, lipid acid, resinous acid, alkylbenzene sulfonate, sulfonated hydrocarbon, vinsol resin, anion surfactant, cats product, nonionogenic tenside, natural rosin, synthetic rosin, inorganic air, synthetic detergent and its corresponding salt, and composition thereof.Air adds with the amount that produces the required air level in cementitious composition.The example that can be used for the air in the admixture system of the present invention includes but not limited to MB AE 90, MB VR and MICRO AIR

, it all can have been bought from joslyn hi-voltage city BASF Admixtures Inc..

The admixture of being concerned about also has defoamer.Defoamer is used for reducing the air content in the cementitious composition.The example that can be used for the defoamer in the cementitious composition includes but not limited to mineral oil, vegetables oil, lipid acid, fatty acid ester, hydroxy functional compound, acid amides, phosphoric acid ester, metallic soap, silicone oil, contains water-insoluble ester, acetylenediol, ethylene oxide-propylene oxide block copolymer and the silicone oil of polymkeric substance, hydrocarbon, alkoxide hydrocarbon, alkoxide polyalkylene oxide, tributyl phosphate, dibutyl phthalate, octanol, carbonic acid and the boric acid of propylene oxide part.

The admixture of being concerned about also has dispersion agent.The term dispersion agent of using in whole specification sheets especially comprises the polycarboxylate salt dispersant who is with or without polyether units.The term dispersion agent also is intended to comprise also those chemical as softening agent, water reducer (as high efficiency water reducing agent), liquid agent, deflocculation agent, or is used for the super plasticizing agent of cementitious composition such as sulfonated lignin, the salt of sulfonation naphthalenesulfonate condensation compound, salt, beta-naphthalenesulfonic-acid salt, sulfonated melamine compound condenses, naphthalene sulfonic acidformaldehyde condensation product resin such as the LOMAR D of sulfonated melamine sulfonate condenses

Dispersion agent (city of Cincinnati, Ohio Cognis Inc.), polyaspartic acid salts or oligopolymer dispersion agent.Can use the polycarboxylate salt dispersant, the polycarboxylate salt dispersant refers to have on the carbon backbone chain dispersion agent of side chain, wherein links to each other with main chain by carboxyl or ether to the small part side chain.Polycarboxylate salt dispersant's example is found in the open 2002/0019459A1 of the U.S., United States Patent (USP) 6,267,814 United States Patent (USP)s 6,290,770, United States Patent (USP) 6,310,143, United States Patent (USP) 6,187,841, United States Patent (USP) 5,158,996, United States Patent (USP) 6,008,275, United States Patent (USP) 6,136,950, United States Patent (USP) 6,284,867, United States Patent (USP) 5,609,681, United States Patent (USP) 5,494,516 United States Patent (USP)s 5,674,929 United States Patent (USP)s 5,660,626, United States Patent (USP) 5,668,195, United States Patent (USP) 5,661,206, United States Patent (USP) 5,358,566, United States Patent (USP) 5,162,402, United States Patent (USP) 5,798,425, United States Patent (USP) 5,612,396, United States Patent (USP) 6,063,184, United States Patent (USP) 5,912,284, United States Patent (USP) 5,840,114, United States Patent (USP) 5,753,744, United States Patent (USP) 5,728,207, United States Patent (USP) 5,725,657, United States Patent (USP) 5,703,174, United States Patent (USP) 5,665,158, United States Patent (USP) 5,643,978, United States Patent (USP) 5,633,298, United States Patent (USP) 5,583,183 and United States Patent (USP) 5,393, in 343, it all is attached to herein by reference, just looks like to have write out fully hereinafter equally.The polycarboxylate salt dispersant who is concerned about includes but not limited to trade mark GLENIUM

3030NS, GLENIUM 3200HES, GLENIUM 3000NS

(joslyn hi-voltage city BASF Admixtures Inc.), ADVA

(Cambridge, Massachusetts city W.R.Grace Inc.), VISCOCRETE

(Zurich, SUI Sika) and SUPERFLUX Dispersion agent or water reducer that (the Axim Concrete Technologies Inc. in Ohio Middlebranch city) sells.

The admixture of being concerned about subtracts the basic active agent in addition.Subtracting the basic active agent can reduce alkali and limit the destructive bulging force that this reaction can produce in maturing.Subtract salt that the basic active agent comprises volcanic ash (flyash, silicon ash), blast-furnace slag, lithium and barium, and other airs.

Can use natural and synthetic admixture look concrete for aesthstic and security reason.Carbon black, ferric oxide, phthalocyanine, umber, chromic oxide, titanium oxide, cobalt blue and organic colorant are often formed and comprised to these painted admixtures by pigment.

The admixture of being concerned about also has corrosion inhibitor.Corrosion inhibitor is used for protecting Embedded Steel to avoid corroding because of concrete height alkalescence in the concrete.Concrete high alkalinity will make and form the non-corrosive protective oxide film of inactive on the reinforcing bar.But carboniogenesis or may destroy or penetrate film and cause corrosion from the existence of the chlorion of deicing agent or seawater.Corrosion inhibition admixture will suppress this corrosion reaction with chemical mode.The most frequently used corrosive material that suppresses is calcium nitrite, Sodium Nitrite, Sodium Benzoate, some vitriol or silicofluoride, fluoaluminate, amine and relevant chemical.

The admixture of being concerned about also has moistureproof admixture.Moistureproof admixture will reduce that cement content is low, the concrete perviousness of shortage fine aggregate in water cement ratio rate height or the aggregate.These admixtures will postpone in the moisture infiltration dry concrete and comprise some soap, stearate and petroleum product.

The gas forming admixture of being concerned about in addition.Foaming agent is that gas formation agent is added in concrete and the mortar so that microdilatancy before the sclerosis with very little amount sometimes.The expansible amount depends on the amount of the used material of getting angry and the temperature of newly mixing compound.Aluminium powder, sodium resinate and plant or gelatin, saponin or protolysate can be used as gas forming admixture.

The permeability reducing agent of being concerned about in addition.Permeability reducing agent is used for reducing under the pressure water transmission by concrete speed.Silicon ash, flyash, ground slag, natural volcanic ash, water reducer and latex can be used to reduce concrete infiltration.

The rheology modifier admixture of being concerned about in addition.Rheology modifier can be used to improve the viscosity of cementitious composition.

Suitable rheology modifier example comprise aerosil, colloidal silica, Natvosol, hydroxypropylcellulose, flyash (such as among the ASTM C618 definition), mineral oil (as the lightweight naphthenic oil), HECTABRITE DP, polyoxyalkylene, polysaccharide, natural gum or its mixture.

The shrinkage-compensating admixture of being concerned about in addition.Spendable shrinkage-compensating agent can include but not limited to RO (AO) in the cementitious composition _1-10(wherein R is C to H _1-5Alkyl or C _5-6Cycloalkyl, A is C _2-3Alkylidene group), alkali metal sulfates, alkaline earth metal sulphate, alkaline earth metal oxide, preferably sulfuric acid sodium and calcium oxide.TETRAGUARD Be an example of economization agent, can have bought from joslyn hi-voltage city BASF Admixtures Inc..

Bacterium and fungi growth can obtain part control by using fungicidal and sterilization admixture on the maturing or in the maturing.The most effective material is many halogenations phenol, Dieldrin-attapulgite mixture emulsion and copper compound for these purposes.

The workability of being concerned about in some embodiment that also has is improved admixture.Its effect of the air of carrying secretly can be used as the workability improving agent just as lubricant.Other workability improving agents are water reducer and some admixture in small, broken bits.

In certain embodiments, cement of the present invention adopts with fiber, for example when the needs fiber reinforced concrete.Fiber can (as polypropylene, nylon, polyethylene, polyester, regenerated fiber, high tenacity aramid (be Kevlar by containing zirconic material, steel, carbon, glass fibre or synthetic materials )) or its mixture make.

The preparation of compositions that the carbon footprint reduces

Aspect of the present invention comprises the method for the concrete composition that preparation carbon footprint reduces.The concrete composition that the carbon footprint reduces can be by at first producing the carbonate component (as CO ₂Cut and to deposit component [being sedimentable matter]), then from described carbonate component (as CO ₂Cutting and to deposit component) concrete composition that reduces of preparation carbon footprint prepares.The carbonate component of the concrete composition that the carbon footprint reduces is (as CO ₂Cut and deposit component) can be from CO ₂The source of source, proton remover (and/or realizing the method that proton is removed) and the source of divalent cation produce, and various described materials will be described in greater detail below.

Carbonic acid gas

Method of the present invention comprises makes a certain amount of divalent cation solution (as the aqueous solution of divalent cation) and CO ₂The source contact makes gained solution stand to promote sedimentary condition then.Method of the present invention also comprises divalent cation solution (as the aqueous solution of divalent cation) and the CO that makes certain volume ₂The source contact also makes this solution stand to promote sedimentary condition simultaneously.Contain in the solution of divalent cation and have the carbonato sedimentable matter (for example from seawater) that enough carbonic acid gas precipitate q.s; But can use other carbonic acid gas.CO ₂The source can be any appropriate C O ₂The source.CO ₂The source can be gas, liquid, solid (as dry ice), supercutical fluid or is dissolved in CO in the liquid ₂In some embodiments, CO ₂The source is gaseous state CO ₂The source.Air-flow can be the CO of substantially pure ₂Or comprise and comprise CO ₂With one or more other gases and/or other materials as ash and other particulates in interior various ingredients.In some embodiments, gaseous state CO ₂The source can be exhaust flow (being the by product of the active procedure of factory) as the exhaust from factory.The character of factory can be different, and factory includes but not limited to power station, chemical processing plant (CPP), mechanical workout factory, refinery, cement mill, steel mill and the by product of act as a fuel burning or other procedure of processings (as the calcining in the cement mill) produces CO ₂Other factories.

Comprise CO ₂Exhaust flow comprise that reductive condition stream (as synthetic gas, conversion synthetic gas, Sweet natural gas, hydrogen etc.) and oxidizing condition flow (stack gas of Tathagata auto-combustion).For the present invention may suitable specific exhaust flow comprise contain oxygen burning factory stack gas (as from coal or other based on the fuel of carbon almost not or without pretreated stack gas), supercharged boiler tail gas, gasification tail gas, conversion gasification tail gas, anaeroic digestor tail gas, well head natural gas flow, reformation Sweet natural gas or methane hydrate etc.Combustion gases from any suitable source all can be used in the method and system of the present invention.Can use the combustion gases in the blowdown stack after the burning of factory such as power station, cement mill and coal source mill in some embodiments.

Therefore, waste streams can produce from the factory of number of different types.The waste streams that suits for the present invention comprises the waste streams that the factory of combustion of fossil fuels (as coal, oil, Sweet natural gas) produces and the artificial fuel Products of naturally occurring organic-fuel mineral deposit (as tar sand, heavy oil, resinous shale etc.).In some embodiments, the waste streams that is suitable for system and method for the present invention can be derived from coal-fired power plant such as fine coal power station, overcritical coal-fired power plant, full dose is burned coal-fired power plant, fluidized bed burned-coal power station; In some embodiments, waste streams can be derived from combustion gas or oil-firing boiler-steam turbine power generation factory, combustion gas or oil-firing boiler simple cycle steam turbine power generation factory or combustion gas or oil-firing boiler combination circulation steam turbine power station.Can use the waste streams of the power station generation of burning synthetic gas (being the gas of the gasification generation of organism such as coal, biomass etc.) in some embodiments.In some embodiments, can use the waste streams that is produced from heat recovery steam generator (HRSG) device by system and method for the present invention.

The waste streams that the cement mill produces also may be suitable for system and method for the present invention.The cement mill waste streams comprises the waste streams from wet method cement factory and nsp cement plant, and described factory can adopt shaft furnace or rotary kiln and can comprise nsp kiln.But each auto-combustion single-fuel of these factories or can be sequential ground or two or more fuel that side by side burn.Other factories such as smeltery and refinery also can be the available sources of carbonated waste streams.

But industrial gaseous waste stream carbonated maybe can contain other components such as oxynitride (NO as the main non-component that is derived from air _X), oxysulfide (SO _X) and one or more other gases, especially under coal-fired power plant's situation.Other gases and other components can comprise CO, mercury and other heavy metals and grit (as from calcining and combustion processes).Other components in the air-flow also can comprise halogenide such as hydrogenchloride and hydrogen fluoride; Particulate matter such as flyash, dust and metal (comprising arsenic, beryllium, boron, cadmium, chromium, chromium VI, cobalt, lead, manganese, mercury, molybdenum, selenium, strontium, thallium and vanadium); With organism such as hydrocarbon, dioxin and PAH compound.In some embodiments, the CO that exists in the suitable off-gas stream that can be treated ₂Amount be 200ppm to 1,000,000ppm, for example 200,000ppm comprises 200 to 1000ppm, 000ppm is to 2000ppm, for example 180,000ppm is to 2000ppm, or 180,000ppm also comprises 180 to 5000ppm, 000ppm to 10,000ppm.Waste streams (the particularly various waste streams of combustion gases) can comprise one or more other components such as water, NO _X(oxynitride: NO and NO ₂), SO _X(oxysulfide: SO, SO ₂And SO ₃), VOC (volatile organic compounds), heavy metal such as mercury and particulate matter (solid particulate or be suspended in liquid in the gas).Effluent gas temperature also can be different.In some embodiments, comprise CO ₂The temperature of stack gas can be 0 ℃ to 2000 ℃, for example 60 ℃ to 700 ℃, comprise 100 ℃ to 400 ℃.

In some embodiments, one or more other components or co-product are (as being used for transforming CO ₂For the product that produces from other parent materials under the same terms of carbonate [as SO _X, NO _XDeng]) precipitable or be trapped in by making the exhaust flow that comprises these other components and comprising divalent cation (as alkaline-earth metal ions such as Ca ²⁺And Mg ²⁺) solution contact in the formed sedimentable matter.The vitriol of calcium and/or magnesium, sulphite etc. are precipitable or be trapped in self-contained SO _X(as SO ₂) the sedimentable matter (also comprising lime carbonate and/or magnesiumcarbonate) that produces of exhaust flow in.Magnesium and calcium can react respectively and form MgSO ₄, CaSO ₄Reach other and contain magnesium and calcareous compound (as sulphite), thereby under the situation of no desulfurized step such as flue gas desulfurization (FGD) (" FGD "), efficiently remove the sulphur in the flue gas stream.Can form CaCO in addition ₃, MgCO ₃Additionally do not discharge CO with related compound ₂Solution at divalent cation contains under the situation of high-content sulphur compound (as vitriol), can make solution be rich in calcium and magnesium so that forming CaSO ₄, MgSO ₄With behind the related compound or except that forming CaSO ₄, MgSO ₄Calcium can be obtained and magnesium forms carbonate cpds with related compound is outer.In some embodiments, the carrying out of desulfurized step can be taken place simultaneously with the precipitation of carbonato sedimentable matter, or desulfurized step can carry out before precipitation.In some embodiments, can collect a plurality of reaction product (as MgCO in different steps ₃, C _aCO ₃, CaSO ₄, aforesaid mixture etc.), and can collect the single reaction product sedimentable matter of carbonate, vitriol etc. (as comprise) in other embodiments.In the step of these embodiments, other components such as heavy metal (as mercury, mercury salt, compound containing mercury) can be trapped within the carbonato sedimentable matter or can precipitate separately.

Can use part off-gas stream (being non-whole off-gas stream) to produce sedimentable matter from factory.In these embodiments, the described part off-gas stream that in the precipitation of sedimentable matter, adopts can be off-gas stream 75% or still less, for example 60% or still less, comprise 50% or still less.Basic (for example 80% or more) the whole off-gas stream that in other embodiments, can adopt in the precipitation of sedimentable matter that factory produces.In these embodiments, 80% of the off-gas stream (as stack gas) that produces of source or more, for example 90% or more, comprise that 95% or more, paramount 100% can be used to the precipitation of sedimentable matter.

Though industrial gaseous waste provides the combustion gas source of higher concentration, method and system of the present invention also can be applicable to remove the combustion gases component from the source (as atmosphere) of the much lower low concentration of contained Pollutant levels ratio such as stack gas.Therefore, in some embodiments, method and system comprises by producing the concentration that stable sedimentable matter reduces pollutent in the atmosphere.In these cases, pollutent such as CO in the part atmosphere ₂Concentration can reduce by 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, 95% or more, 99% or more, 99.9% or more or 99.99%.This reduction of atmospheric polluting material is productive rate (yield) or higher or lower productive rate realization as described herein, and can realize in a settling step or a series of settling step.

Divalent cation

Method of the present invention comprises divalent cation solution (as the aqueous solution of divalent cation) and the CO that makes certain volume ₂The source contact also makes gained solution stand to promote sedimentary condition.In some embodiments, can make the divalent cation solution (as the aqueous solution of divalent cation) and the CO of certain volume ₂The source contact also makes this solution stand to promote sedimentary condition simultaneously.Divalent cation can depend on the availability at place, locality from any a large amount of different divalent cation sources.This class source comprises industrial waste, seawater, salt solution, hard water, rock and mineral (as lime, periclasite, the material that comprises metal silicate such as serpentine and peridotites) and any other suitable source.

In some places, will provide the source of suitable divalent cation (and process in available other materials such as metal hydroxides) sometimes from the industrial waste stream of various commercial runs.This class waste streams includes but not limited to Mining wastes; Combustion of fossil fuel ashes (as ashes such as flyash, furnace bottom ash, the boiler slag of burning); Slag (as scum, phosphorus slag); The cement kiln refuse; Refinery/petrochemical refinery factory refuse (as oil field and methane ore bed salt solution); Colliery layer refuse (as gas production salt solution and colliery layer salt solution); The paper conversion refuse; Water softening effluent brine (as ion-exchange waste water); Silicon processing refuse; Agricultural waste; Metal finishing refuse; High pH weaving refuse; And alkaline residue.Combustion of fossil fuel ashes, cement kiln dust and slag (general designation metal oxide source of waste) are also seen the U.S. Patent application 12/486,692 that is set forth in submission on June 17th, 2009, and it openly is attached to herein by reference.Can be and implement purpose of the present invention and mix and assist and join any divalent cation source of description herein.For example, can be implement purpose of the present invention and with the material that comprises metal silicate (as serpentine, peridotites) that further describes in the U.S. Patent application of submitting on July 10th, 2,009 12/501,217 (this application is attached to herein by reference) with described any divalent cation source is combined herein.

In some places, for carbonate of the present invention (as CO ₂Cut and to deposit component) preparation and stark suitable divalent cation source can be the water aqueous solution such as the seawater or the face of land salt solution of divalent cation (as comprise), it can be different with implementing locality of the present invention.The suitable divalent cation solution of available comprises and comprises one or more divalent cations for example alkaline earth metal cation such as Ca ²⁺And Mg ²⁺The aqueous solution.In some embodiments, the aqueous solution of divalent cation comprises alkaline earth metal cation.In some embodiments, alkaline earth metal cation comprises calcium, magnesium or its mixture.In some embodiments, the aqueous solution packet content of divalent cation is 50-50,000ppm, 50-40,000ppm, 50-20,000ppm, 100-10, the calcium of 000ppm, 200-5000ppm or 400-1000ppm.In some embodiments, the aqueous solution packet content of divalent cation is 50-40,000ppm, 50-20,000ppm, 100-10,000ppm, 200-10, the magnesium of 000ppm, 500-5000ppm or 500-2500ppm.Ca therein ²⁺In some embodiments that all exist with Mg2+, Ca in the aqueous solution of divalent cation ²⁺To Mg ²⁺Ratio (be Ca ²⁺: Mg ²⁺) can be 1: 1-1: 2.5,1: 2.5-1: 5,1: 5-1: 10,1: 10-1: 25,1: 25-1: 50,1: 50-1: 100,1: 100-1: 150,1: 150-1: 200,1: 200-1: 250,1: 250-1: 500,1: 500-1: 1000 or its scope in.For example, in some embodiments, Ca in the aqueous solution of divalent cation ²⁺To Mg ²⁺Ratio can be 1: 1-1: 10,1: 5-1: 25,1: 10-1: 50,1: 25-1: 100,1: 50-1: 500 or 1: 100-1: 1000.In some embodiments, Mg in the aqueous solution of divalent cation ²⁺To Ca ²⁺Ratio (be Mg ²⁺: Ca ²⁺) can be 1: 1-1: 2.5,1: 2.5-1: 5,1: 5-1: 10,1: 10-1: 25,1: 25-1: 50,1: 50-1: 100,1: 100-1: 150,1: 150-1: 200,1: 200-1: 250,1: 250-1: 500,1: 500-1: 1000 or its scope in.For example, in some embodiments, Mg in the aqueous solution of divalent cation ²⁺To Ca ²⁺Ratio can be 1: 1-1: 10,1: 5-1: 25,1: 10-1: 50,1: 25-1: 100,1: 50-1: 500 or 1: 100-1: 1000.

The aqueous solution of divalent cation can comprise and is derived from the divalent cation that fresh water, slightly salty, seawater or salt solution (as naturally occurring salt solution or artificial salt solution such as ground heat plant waste water, desalination plants waste water) and other salinity are higher than the salt water of fresh water, and wherein any described water can be naturally occurring or artificial.Slightly salty is more salty but not as the salty water of seawater than fresh water.The salinity of slightly salty arrives in about 35ppt (permillage) scope about 0.5.Seawater is the water from sea, ocean or any other salt water, and its salinity arrives in about 50ppt scope about 35.Salt solution is saturated by salt or approaching saturated water.The brinish salinity is about 50ppt or higher.In some embodiments, the water source that divalent cation was derived from is for being rich in the freshwater source of mineral (as be rich in calcium and/or be rich in magnesium).In some embodiments, the water source that divalent cation was derived from can be naturally occurring salt water source, and described salt water source is selected from sea, ocean, lake, marsh, river mouth, lagoon, face of land salt solution, dark salt solution, alkaline lake, inland sea etc.In some embodiments, the water source that divalent cation was derived from can be the artificial salt solution that is selected from ground heat plant waste water or desalination waste water.

Fresh water can be suitable divalent cation (as alkaline earth metal cation such as Ca ²⁺And Mg ²⁺) the source.Can use in any a large amount of suitable freshwater source, comprise from the source of not having mineral to the freshwater source in the source of being rich in mineral.The freshwater source that is rich in mineral can be naturally occurring, comprises a large amount of hard water source, lake or interior marine any.Some are rich in the freshwater source of mineral such as alkali lake or inland sea (as osmanli all lakes) also provides pH-to change the source of agent.The freshwater source that is rich in mineral also can be artificial.For example, can make the poor water (soft water) that contains mineral and divalent cation such as alkaline earth metal cation (as Ca ²⁺, Mg ²⁺Deng) source contact be suitable for the water that is rich in mineral of described method and system herein with generation.The available any suitable scheme of divalent cation or its precursor (as salt, mineral) (as adding solid, suspension or solution) is added in the fresh water water of any other type (or herein).In some embodiments, can in fresh water, add and be selected from Ca ²⁺And Mg ²⁺Divalent cation.In some embodiments, be selected from Na ⁺And K ⁺Monovalent cation be added in the fresh water.In some embodiments, can Ca will be comprised ²⁺Fresh water and burning ashes (as flyash, furnace bottom ash, boiler slag) or its goods or form processing combination, thereby produce the solution that comprises calcium and magnesium cation.

In some embodiments, the aqueous solution of divalent cation can obtain from the factory that combustion gas flowing also is provided.For example, in water-cooled factory such as cooled with seawater factory, being used for refrigerative water by factory can be then as the water that produces sedimentable matter.If desired, described water can be through cooling before entering settling system of the present invention.This method can for example be used for once-through cooling system.For example, city or agriculture water source of supply can be used as the once-through cooling system of factory.Water from factory can be used for producing sedimentable matter then, and wherein exporting glassware for drinking water has the hardness of reduction and the purity of Geng Gao.

The method that proton remover and realization proton are removed

Method of the present invention comprises divalent cation solution (as the aqueous solution of divalent cation) and the CO that makes certain volume ₂The source contact is (with dissolving CO ₂) and make gained solution stand to promote sedimentary condition.In some embodiments, can make the divalent cation solution (as the aqueous solution of divalent cation) and the CO of certain volume ₂The source contact is (with dissolving CO ₂) and make this solution stand to promote sedimentary condition simultaneously.CO ₂Dissolving in divalent cation solution will produce carbonic acid, and carbonic acid is the material type (species) with supercarbonate and carbonate eqrilibrium.For producing carbonato sedimentable matter, should remove proton and balance is moved to carbonate by the various material types (as carbonic acid, supercarbonate, oxonium ion etc.) from the solution that contains divalent cation.Along with proton is removed, more CO ₂To enter in the solution.In some embodiments, the solution that the contains divalent cation aqueous solution of divalent cation (as comprise) and CO can be made ₂Use proton remover and/or method to increase a CO in the precipitin reaction stage during contact ₂Absorb, wherein pH can keep constant, raise or even reduce, the quick removal (for example by adding alkali) that is proton then is so that carbonato sedimentable matter rapid precipitation.Can remove proton from various material types (as carbonic acid, supercarbonate, oxonium ion etc.) by any method easily, include but not limited to use naturally occurring proton remover, use microorganism and fungi, use synthetic proton to remove chemical agent, reclaim artificial waste streams and use electrochemical means.

Naturally occurring proton remover is included in any proton remover that can find in the more wide environment that can produce or have alkaline local environment.Some embodiments provide naturally occurring proton remover, comprise when being added in the solution will living alkaline environment mineral.These class mineral include but not limited to lime (CaO), periclasite (MgO), ironic hydroxide mineral (as pyrrhosiderite and limonite) and volcanic ash.These class mineral will be provided herein and comprise the digestion procedure of the rock of these class mineral.Some embodiments provide the water body that uses natural alkalescence as naturally occurring proton remover.The example of the water body of natural alkalescence includes but not limited to earth surface water source (as the Mono lake in alkali lake such as California) and underground water source (as the dark geology alkalescence aqueous stratum of alkaline aqueous stratum as the Sai Ersi Hu Chu that is positioned at California).Other embodiments provide the settling of the dried alkaline water body of controlling oneself as the sedimental use in the Natron lake of rift valley greatly along Africa.In some embodiments, can use the organism of in its eubolism secreted alkaline molecule or solution as the proton remover.The example of this class organism has the bacterium (as the Lyngbya sp. of cyanobacteria Tathagata from the Atlin of British Columbia wetland, it increases pH because of photosynthetic by product) of the fungi that produces Sumizyme MP (be as best pH 9 deep-sea fungi Aspergillus ustus) and the alkaline molecule of generation.In some embodiments, can use organism to produce the proton remover, wherein organism (for example Bacillus pasteurii, it will make hydrolysis of urea is ammonia) will make pollutent (as urea) metabolism produce the proton remover or comprise the solution (as ammonia, ammonium hydroxide) of proton remover.In some embodiments, but organism autoprecipitation reaction mixture single culture, and the solution that wherein uses the proton remover or comprise the proton remover is to add in the precipitin reaction mixture.In some embodiments, can use naturally occurring in combination with the proton remover or the synthetical enzyme to cause the precipitation of sedimentable matter.Carbonic anhydrase (it is the enzyme that plant and animal produces) will speed up in the solution carbonic acid to the conversion of supercarbonate.Therefore, carbonic anhydrase can be used to strengthen CO ₂Dissolving and the precipitation of accelerate precipitation material, described in the U.S. Provisional Patent Application of submitting on October 19th, 2,009 61/252,929, this patent application is attached to herein by quoting in full.

Be used for realizing that the chemical agent that proton is removed is often referred to mass production and the commercially available synthetic chemistry agent that gets.For example, the chemical agent that is used to remove proton includes but not limited to oxyhydroxide, organic bases, super base, oxide compound, ammonia and carbonate.Oxyhydroxide is included in the chemical substance that hydroxide anion is provided in the solution, comprises for example sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca (OH) ₂) or magnesium hydroxide (Mg (OH) ₂).Organic bases is common carbon-containing molecules as nitrogenous base, comprises primary amine (as methylamine), secondary amine (as Diisopropylamine), tertiary amine (as diisopropylethylamine), arylamine (as aniline), heteroaromatics (as pyridine, imidazoles and benzoglyoxaline) and various forms thereof.In some embodiments, can use the organic bases that is selected from pyridine, methylamine, imidazoles, benzoglyoxaline, Histidine and phosphine nitrile to remove proton to impel the precipitation of sedimentable matter from various material types (as carbonic acid, supercarbonate, oxonium ion etc.).In some embodiments, can use ammonia to promote pH to the level that is enough to sediment matter from the solution of divalent cation and industrial waste stream.The super base that is suitable for use as the proton remover comprises sodium ethylate, sodium amide (NaNH ₂), sodium hydride (NaH), butyllithium, lithium diisopropylamine, diethylamino lithium and two (trimethyl silyl) Lithamide.Oxide compound comprises that for example calcium oxide (CaO), magnesium oxide (MgO), strontium oxide (SrO), beryllium oxide (BeO) and barium oxide (BaO) may also be spendable suitable proton removers.Be used for carbonate of the present invention and include but not limited to yellow soda ash.

The suitable metallic forms of the positively charged ion of being concerned about except that comprising and other, also can provide the proton remover from the waste streams of various commercial runs.This class waste streams includes but not limited to Mining wastes; Combustion of fossil fuel ashes (as ashes such as flyash, furnace bottom ash, the boiler slag of burning); Slag (as scum, phosphorus slag); The cement kiln refuse; Refinery/petrochemical refinery factory refuse (as oil field and methane ore bed salt solution); Colliery layer refuse (as gas production salt solution and colliery layer salt solution); The paper conversion refuse; Water softening effluent brine (as ion-exchange waste water); Silicon processing refuse; Agricultural waste; Metal finishing refuse; High pH weaving refuse; And alkaline residue.Mining wastes comprise coming any refuse when extracting metal or other preciousnesses or valuable mineral in soil.In some embodiments, can be used to change pH from the refuse of digging up mine, wherein said refuse is selected from the red soil from Bayer aluminium extraction process; Refuse when coming in seawater, to extract magnesium (Mg (OH) for example ₂, as the Mg (OH) that finds at the Moss in California Landing ₂); With from the refuse that relates to the molten mining technology that soaks.For example, red soil can be used for changing pH described in the U.S. Provisional Patent Application of submitting on March 18th, 2,009 61/161369, and described patent application is attached to herein by quoting in full.Can use combustion of fossil fuel ashes, cement kiln dust and slag (general designation metal oxide source of waste) so that proton remover of the present invention to be provided in combination separately or with other proton removers, also see and be set forth in the U.S. Patent application of submitting on June 17th, 2,009 12/486,692, the open of described patent application is attached to herein by quoting in full.Agricultural waste (from animal waste or excessively fertilizer use) may contain potassium hydroxide (KOH) or ammonia (NH ₃) or the two.Therefore, in some embodiments of the present invention, agricultural waste can be used as the proton remover.Described agricultural waste often concentrate in the pond, but its also diafiltration downwards advance in the aqueous stratum and obtain thus and use.

Electrochemical method can be another approach that various species from solution are removed protons, described approach or remove proton from solute (as the deprotonation of carbonic acid or supercarbonate) or from solvent (as the deprotonation of oxonium ion or water).If from CO ₂The proton that produced of dissolving and the proton of removing from solute molecule by electrochemical method quite or surpass the proton of removing then can obtain the result of solvent deprotonation.In some embodiments, can use the low voltage electrochemical method to come for example with CO ₂Be dissolved in the precipitin reaction mixture or the precursor solution of precipitin reaction mixture (can or can not contain the solution of divalent cation) in and remove proton.In some embodiments, be dissolved in CO in the solution that does not contain divalent cation ₂Available low voltage electrochemical method is handled with from carbonic acid, supercarbonate, oxonium ion or because of CO ₂Any substance classes of producing of dissolving or its combination in remove proton.The low voltage electrochemical method is 2,1.9,1.8,1.7 or 1.6V or lower, for example 1.5,1.4,1.3,1.2, move under 1.1V or lower, for example 1V or lower, for example 0.9V or lower, 0.8V or lower, 0.7V or lower, 0.6V or lower, 0.5V or lower, 0.4V or lower, 0.3V or lower, 0.2V or lower or 0.1V or the lower average voltage.The low voltage electrochemical method that does not produce chlorine may be suitable for use in the system and method for the present invention.The low voltage electrochemical method of not oxygenous removal proton may also be suitable for use in the system and method for the present invention.In some embodiments, the low voltage electrochemical method will produce hydrogen and transport hydrogen to anode at the negative electrode place, and described hydrogen is converted into proton at anode.The electrochemical method that does not produce hydrogen may also be suitable.Sometimes, the electrochemical method of removal proton will not produce any gaseous by-product.The electrochemical method that the realization proton is removed is also seen the U.S. Patent application 12/344 that is set forth in submission on December 24th, 2008,019, the U.S. Patent application of submitting on December 23rd, 2,008 12/375,632, the International Patent Application PCT/US09/32301 that submits in the International Patent Application PCT/US08/088242 that submitted on December 23rd, 2008, on January 28th, 2009, International Patent Application PCT/US09/48511 that on June 24th, 2009 submitted to and the U.S. Patent application of submitting on August 13rd, 2,009 12/541,055, it respectively is attached to herein by quoting in full.

Perhaps, can use electrochemical method to pass through for example chlor-alkali or its modification generation causticity molecule (as oxyhydroxide).Electrode (being negative electrode and anode) can be present in the solution that contains divalent cation or charge into off-gas stream and (as charged into CO ₂) the device of solution in, electrode as described in the selectivity barrier can be separated as film.The electro-chemical systems and the method that are used to remove proton can produce by product (as hydrogen), and described by product can be collected and be used for other purposes.Other electrochemical methods of available include but not limited to the U.S. Provisional Patent Application 61/081 that on July 16th, 2008 submitted in the system and method for the present invention, 299 and U.S. Provisional Patent Application 61/091, those that describe in 729, the open of described patent application is attached to herein by reference.The combination that can adopt proton remover above-mentioned source and effectively remove the method for proton.

Can adopt multiple diverse ways to come from CO ₂Source, divalent cation source and proton remover source prepare concrete CO of the present invention ₂Cut and deposit component.The CO that is concerned about ₂Cut the scheme of depositing include but not limited in the following patent application disclosed those: U.S. Patent application 12/126,776 and 12/163,205; And 29,12/344,019 and 2009 on Mays of submitting to 24,12/163,205,2008 on December that the U.S. Provisional Patent Application submitted to was submitted at June 27 in 61/126,776,2008 on May 23rd, 2008 submit to 12/475,378; And U.S. Provisional Patent Application 61/017,405,61/017,419,61/057,173,61/056,972,61/073,319,61/079,790,61/081,299,61/082,766,61/088,347,61/088,340,61/101,629; With 61/101 of submission on December 28th, 2007,631017,405,61/017 of submission on December 28th, 2007,419,61/057 of submission on May 29th, 2008,173,61/056 of submission on May 29th, 2008,972,61/073 of submission on June 17th, 2008,319,61/079 of submission on July 10th, 2008,790,61/081,299 of submission on July 16th, 2008,61/082,766 of submission on July 22nd, 2008,61/088 of submission on August 13rd, 2008,347,61/088 of submission on August 12nd, 2008,340,61/101,631 of the submission of submitting on September 30th, 2008 in 30,61/101,629 and 2008 on September; It respectively is attached to herein by reference.

CO of the present invention ₂Cut and to deposit the component component of carbonate, supercarbonate or its combination (as comprise) and comprise carbonate salt composition, described carbonate salt composition can be by producing from the solution precipitation calcium of divalent cation and/or the carbonate salt composition of magnesium.Carbonate cpds composition of the present invention contains sedimentary crystallization and/or decolorizing carbon phosphate compounds.Constitute CO of the present invention ₂Cut the carbonate cpds composition deposit the component component of carbonate, supercarbonate or its combination (as comprise) and contain metastable carbonate cpds, described metastable carbonate cpds can precipitate from the solution such as the salt water of divalent cation, and this will be described in greater detail below.

For simplicity, describe with salt water sometimes herein; But should understand any water source that comprises divalent cation all can use.The carbonate cpds composition that is derived from salt water of the present invention (promptly be derived from salt water and by one or more different carbonate crystallizations and/or amorphous compound adds or do not add one or more crystallizations or composition that amorphous hydroxide constituted) is derived from salt water.Therefore, it comprises in a certain way the composition that obtains from salt water, for example by to be enough to handle from the mode that initial salt water volume produces required carbonate cpds composition the composition that salt water was obtained of certain volume.The carbonate cpds composition of some embodiment can produce by divalent cation solution (as the salt water) precipitation from alkaline including earth metal positively charged ion such as calcium and magnesium etc., and wherein this class divalent cation solution can be referred to as the water of alkaline including earth metal.

The salt water that adopts in the method can be different.As mentioned above, the salt water of being concerned about comprises that slightly salty, seawater and salt solution and other salinity are higher than the salt water of fresh water (its salinity is lower than the 5ppt dissolved salt).In some embodiments, the calcareous water of richness and Magnesium Silicate q-agent mineral such as peridotites or serpentine can formed carbonic acid and become in the tart solution and making up because of adding carbonic acid gas, described solution will dissolve Magnesium Silicate q-agent, thereby cause the formation of silicic acid miemite compound as mentioned above.

In producing carbonate cpds method for compositions of the present invention, can make the water of certain volume stand to be enough to produce the carbonate cpds deposition condition of carbonato sedimentable matter and mother liquor (promptly being settled out remaining portion water behind the carbonate cpds) from salt water.Gained sedimentable matter and mother liquor constitute carbonate cpds composition of the present invention together.Any suitable deposition condition all can adopt, and described condition causes the carbonate cpds composition to cut the generation of depositing goods.

Promote that sedimentary condition (being deposition condition) can be different.For example, the temperature of water can be in the optimum range that the precipitation of being convenient to required mineral takes place.In some embodiments, the temperature of water can be in 5-70 ℃ of scope, for example 20-50 ℃, comprises 25-45 ℃.Therefore, though the set of the deposition condition of giving can have 0-100 ℃ temperature range, the temperature of adjustable water saving in certain embodiments is to produce required sedimentable matter.

In common seawater, 93% dissolving CO ₂Can be bicarbonate ion (HCO ₃ ^-) form, 6% can be carbonate ion (CO ₃ ^2-) form.When from common seawater precipitated chalk, will discharge CO ₂In fresh water, when pH is higher than 10.33, the carbonate above 90% will be the form of carbonate ion and do not have CO in the precipitation process of lime carbonate ₂Discharge.In seawater, this changes at low slightly pH (more near 9.7 pH) and takes place down.In set precipitation process, though the pH of the water that adopts in the method can be promoted to pH alkaline level to drive the precipitation of carbonate cpds and other compounds such as oxyhydroxide in certain embodiments as required at pH5 in the pH14 scope.In some these embodiment, pH can be promoted to and make CO in the precipitation process ₂Generation minimize the level of (if not the words of eliminating), thereby make for example with carbonate and bicarbonate form dissolved CO ₂Be trapped within the sedimentable matter.In these embodiments, pH can be promoted to 10 or higher, for example 11 or higher.

The pH of water can promote with any suitable method.Can adopt the proton remover in certain embodiments, wherein the example of this class reagent comprises that oxide compound, oxyhydroxide are (as the calcium oxide in the flyash, potassium hydroxide, sodium hydroxide, brucite Mg (OH) ₂Deng), carbonate (as yellow soda ash) etc., they are many describes in the above.These class methods of the pH of a kind of lifting precipitin reaction mixture or its precursor solution of divalent cation (as contain) are to use the coal ash from coal-fired power plant, and described coal ash contains many oxide compounds.Other coals are handled as coal gasification (to produce synthetic gas) and are also produced hydrogen and carbon monoxide and also can be used as hydroxide source.Some naturally occurring mineral such as serpentine contain oxyhydroxide and solubilized to produce hydroxide source.The adding of serpentine also discharges silicon-dioxide and magnesium in solution, thereby causes the formation of silica containing sedimentable matter.The amount that is added to the proton remover in precipitin reaction mixture or its precursor should depend on the specific nature of proton remover and the amount of reformed precipitin reaction mixture or its precursor, and should be enough to promote the pH of precipitin reaction mixture or its precursor to required pH.Perhaps, the pH of precipitin reaction mixture or its precursor can be promoted to desired level by electrochemistry approach as mentioned above.Can use other electrochemical methods under certain conditions.For example, electrolysis be can adopt, mercury cell method (also claiming the Castner-Kellner method), diaphragm cell method, membrane electrolytic cell method or its some combinations wherein can be used.When needs, can collect and adopt the by product such as the H of hydrolysate as required for other purposes ₂, sodium Metal 99.5 etc.

In other embodiments, can adopt the U.S. Provisional Patent Application of submitting on July 16th, 2,008 61/081,299 and submitted on August 25th, 2008 61/091,729 described in the pH-method for improving, it is open to be attached to herein by reference.

Also but Xiang Shuizhong introduces the character that the additive that is different from the pH-elevator influences the sedimentable matter that is produced.Therefore, some embodiment of method of the present invention is included in when water stands deposition condition and provides additive before or in the process in water.Some additive of trace can be facilitated some calcium carbonate polycrystalline type thing.For example, can obtain veterite with very high productive rate by introduce trace lanthanum such as Lanthanum trichloride in the supersaturated solution of lime carbonate, veterite is the unsettled CaCO of a kind of height ₃Polymorphic form, it will and change calcite rapidly into multiple different forms precipitation.Other additives of also being concerned about except that lanthanum comprise but are not limited to transition metal etc.For example, the known formation that will help unordered rhombspar (protodolomite) of adding ferrous or iron ion, otherwise can not form.

Also can influence the character of sedimentable matter by the leading ion ratio of selecting to suit.The leading ion ratio also has considerable influence to the formation of polymorphic form.For example, along with magnesium in the water: calcium ratio increases, and aragonite will become the calcium carbonate polycrystalline type thing more favourable than low-Mg calcite.At lower magnesium: under the calcium ratio, low-Mg calcite may be preferred polymorphic form.Therefore, can adopt magnesium widely: calcium ratio comprises for example 100: 1,50: 1,20: 1,10: 1,5: 1,2: 1,1: 1,1: 2,1: 5,1: 10,1: 20,1: 50,1: 100 or any above-mentioned ratio.In certain embodiments, magnesium: calcium ratio can be determined by the water source that adopts in the precipitation process (as seawater, salt solution, slightly salty, fresh water), and in other embodiments, magnesium: calcium ratio can be adjusted in certain scope.

Settling rate also has a significant impact the formation mutually of compound.The fastest precipitation can obtain by making the solution crystallization with required phase.During crystallization, rapid precipitation can not obtain by the pH of fast lifting seawater, and this will cause more unbodied component.When having silicon-dioxide, speed of reaction is fast more, will be incorporated into more silicon-dioxide in the then carbonato sedimentable matter.PH is high more, precipitation will be fast more and sedimentable matter will be amorphous more.

Therefore, in certain embodiments, the deposition condition set that produces required sedimentable matter from the solution of divalent cation comprises the temperature and the pH of water, and comprises the concentration of additive and the ionic species in the water sometimes.Deposition condition also can comprise form (as ultrasonic), brilliant existence, catalyzer, film or the base material of kind of factor such as mixing rate, stirring.In some embodiments, deposition condition comprises supersaturated condition, temperature, pH and/or concentration gradient or circulation or changes any of these parameter.The method that is used for preparing according to carbonato sedimentable matter of the present invention can be interrupter method or continuous processing.Should be understood that the set required deposition condition of sedimentable matter of generation may be with different in batch system in continuous-flow system.

In certain embodiments, described method also comprises water and the CO that makes the volume that stands the mineral precipitation condition ₂The source contact.Described water and CO ₂The contact in source can stand CO at Dang Shui ₂Carry out before during deposition condition and/or in the process.Therefore, embodiment of the present invention comprise that the water of wherein said volume can stand before the mineral precipitation condition at the salt water of described volume and CO ₂The method of source contact.Embodiment of the present invention comprise that the salt water of wherein said volume can be when the decent carbonate suspension compound precipitation of the salt water of described volume condition and CO ₂The method of source contact.Embodiment of the present invention comprise that the water of wherein said volume can stand before the carbonate cpds deposition condition at the salt water of described volume and during the decent carbonate suspension compound precipitation of the salt water condition of described volume and CO ₂The method of source contact.In some embodiments, identical water is capable of circulation to be surpassed once, wherein the first precipitation circulation is mainly removed lime carbonate and magnesiumcarbonate mineral and is stayed remaining alkaline water, can in described alkaline water, add other and can allow more carbonic acid gas round-robin source of alkaline earth metal therein, thereby be settled out more multi-carbonate compound.

The CO that can contact in these embodiments with the salt water of described volume ₂The source can be any suitable CO ₂Source, contact method can be any suitable method.Work as CO ₂During for gas, the contact method of being concerned about includes but not limited to: contact method (as to as described in the salt water bubbling of volume), following current route of exposure (being to contact between gas and the liquid phase stream of uniflux), adverse current approach (being to contact between gas and the liquid phase stream of reversed flow) etc.Therefore, contact can be according to conformance by using realizations such as injector, bubbler, fluid Venturi reactor, sparger, gas filter, spraying, column plate or packing tower reactor.For the solution and the CO that are used to make divalent cation ₂The example system and the method for source contact, referring to the U.S. Provisional Patent Application of submitting on March 10th, 2,009 61/158,992,61/168 of submission on April 9th, 2009,166,61/228 of the submission of submitting to 14,61/170,086,2009 on Mays of submitting on April 16th, 2009 in 24,61/178,475,2009 on July, 210,61/230 of submission on July 30th, 2009,61/239,429 of submission on September 2nd, 042 and 2009, it respectively is attached to herein by reference.

Top method will produce the carbonate sedimentable matter (as CO ₂Cut and to deposit sedimentable matter) and the slurry of mother liquor.When needing, can before post precipitation and further processing, store for some time by the composition that sedimentable matter and mother liquor constitute.For example, described composition can be stored 1-1000 days under the temperature of 1-40 ℃, for example 20-25 ℃ or longer, for example 1-10 sky or longer time.

Separable then slurry components.Embodiment can comprise that mother liquor handles, and wherein said mother liquor can or can not be present in the same composition as goods.For example, when mother liquor will be returned the ocean, can make mother liquor and gaseous state CO ₂The source contacts in the mode of the concentration that is enough to improve the carbonate ion that exists in the mother liquor.Contact available any suitable method and carry out, for example described above those.In certain embodiments, mother liquor has alkaline pH, with CO ₂The contact in source can be enough to reduce pH to 5-9, for example 6-8.5, comprise that the mode of the scope of 7.5-8.2 carries out.In certain embodiments, can make treated salt solution and for example CO as mentioned above ₂The source contact is deposited more CO to cut ₂For example, when mother liquor will be returned the ocean, can make mother liquor and gaseous state CO ₂The source contacts in the mode of the concentration that is enough to improve the carbonate ion that exists in the mother liquor.Contact available any suitable method and carry out, for example described above those.In certain embodiments, mother liquor has alkaline pH, with CO ₂The contact in source can be enough to reduce pH to 5-9, for example 6-8.5, comprise that the mode of the scope of 7.5-8.2 carries out.

The gained reaction mother liquor can be disposed with any suitable method.In certain embodiments, it can be sent to tailing pond to dispose.In certain embodiments, it can be disposed in naturally occurring water body Ru Hai, ocean, lake or river.In certain embodiments, mother liquor is returned the water-supply source of method of the present invention as ocean or extra large.Perhaps, mother liquor can be further processed, and for example stands the desalination program, and this further describes in U.S. Patent application 12/163,205, and it openly is attached to herein by reference.

In certain embodiments, producing sedimentable matter (as CO ₂Cut and deposit component) after, the gained material can be separated with mother liquor to produce isolating sedimentable matter (as CO ₂Cut and deposit goods).Sedimentable matter is (as CO ₂Cut and to deposit component) the available any suitable method of separation reach, comprise mechanical means, for example wherein a large amount of excessive water by for example gravity self or apply the vacuum machine extruding from sedimentable matter discharge, by producing filtrate etc. from mother liquor filtering-depositing material.In certain embodiments, the separation of big water gaging will produce wet dehydration lees matter.

Gained dehydration lees matter can be dry as required then to produce dry article.Dry can the realization by the wet sedimentable matter of dry air.When wet sedimentable matter during through dry air, dry air can be carried out under room temperature or high temperature.In another embodiment, wet sedimentable matter can be spray-dried with drying precipitated material, the liquid that wherein contains sedimentable matter is dry by the hot gas (the off-gas stream of the spontaneous power plant of Tathagata) that flows through is provided, and for example wherein liquid feeding is pumped through spraying gun and enters in the main kiln and hot gas passes through as the following current or the adverse current of spraying gun direction.According to the specific drying means of system, dry station can contain filtering element, lyophilize structure, spraying drying structure etc.When needing, dehydration lees matter goods can be through washing before dry.Sedimentable matter can be with the fresh water washing for example to remove desalt (as NaCl) from dehydration lees matter.

In certain embodiments, before use subsequently, can make with extra care (i.e. processing) sedimentable matter in a certain way.Make with extra care and to comprise multiple diverse ways.In certain embodiments, product can stand machine finish as grinding to obtain to have the goods of required physical properties such as particle diameter etc.

In some embodiments, product can be used as " supplementary cementitious material " (SCM).Though SCMs for himself can be or can not be the hydraulic gelling will be to a certain extent produce those materials of hardened material with hydraulic cement compositions such as portland cement reaction.The example that is used for the common SCMs of portland cement composition comprises flyash and levigate granulated blast-furnace slag.

In certain embodiments, product can be used to produce aggregate.The gained sedimentable matter can be then through or be prepared as aggregate without dried powder.Produce in some embodiment of particulate of desired size in drying process, for producing aggregate, substantially (if any) do not need overwork.And in other embodiments, can further process to produce required aggregate sedimentable matter.For example, as mentioned above, sedimentable matter and fresh water can be made up in the mode that is enough to make sedimentable matter form solid product, the metastable carbonate cpds that wherein exists in the sedimentable matter has been converted into form stable in fresh water.By the water content of control wet feed, the porosity of the final aggregate of may command and final strength and density.Usually, wet cake will contain the water of 40-60% volume.For fine and close aggregate, wet cake will contain＜50% water, and for more unsound cake, wet cake will contain＞50% water.After the sclerosis, the gained solid product can be then through mechanical workout as crushing or otherwise smash and store the aggregate that has required feature such as size, specified shape etc. with generation.In these processes, solidify with mechanical processing steps and can carry out in a substantially continuous manner or in the isolating time.In certain embodiments, a large amount of sedimentable matters can being stored in wherein, sedimentable matter will be exposed in the atmospheric open environment.For coagulation step, can suitable mode water fresh water to sedimentable matter, maybe can allow it drench with rain naturally to produce solidification products.Solidification products can be then as mentioned above through mechanical workout.After sedimentable matter produces, can process sedimentable matter to produce required aggregate.In some embodiments, sedimentable matter can be left on the open air, and here, rainwater can be used as freshwater source so that the atmospheric water stabilization reactions to take place, and forms aggregate thereby sedimentable matter is hardened.

In the example of one embodiment of the invention, sedimentable matter can spread into uniform mode machinery on the ground of compacting to two inches of the degree of depth of being concerned about such as height to ten with endless belt conveyor and road scraper, and for example the 1-12 inch comprises the 6-12 inch.The ratio of ratio that can be suitable such as every cubic feet of sedimentable matter of pottle water is to sprawling material pouring fresh water then.Those that use in available then Steel Roller such as the pitch compacting are repeatedly tamped.Can water the surface weekly once more and present required chemistry and mechanical property until material, can be processed into aggregate with material mechanical this moment by crushing.

In the example of another embodiment of the present invention, the carbonate cpds sedimentable matter can place pressure filter to produce and contain 30-60% solid filter cake then separating the back with the fresh water washing with mother liquor.This filter cake can be then with any suitable measure such as hydropress in 5-1000psi for example, as the enough pressure of 1-200psi under in mould mechanical presses to produce formation solid such as straight brick.These solids of gained can be then by for example place the outside store, by placing the sclerosis such as indoor that stands high humidity and temperature.These hard solids of gained can be used as material of construction self then or crush to produce aggregate.Further describe in the U.S. Patent application 61/056,972 of such aggregate, its Manufacturing approach and use pending trial when on May 29th, 2008 submitted to, it openly is attached to herein by reference.

Fig. 1 has provided the carbonate that produces according to one embodiment of the invention (as CO ₂Cut and to deposit component) the indicative flowchart of method.In Fig. 1, stand the carbonate cpds deposition condition at settling step 120 places from the divalent cation in divalent cation source 110.As mentioned above, salt water refers to any in some dissimilar non-fresh bodies, comprises that slightly salty, seawater and salt solution (comprising artificial salt solution such as ground heat plant waste water, desalination waste water etc.) and other salinity are higher than the salt water of fresh water.The salt water source that the carbonate cpds composition of cement of the present invention can be derived from can be naturally occurring source Ru Hai, ocean, lake, marsh, river mouth, lagoon etc. or artificial source.

In certain embodiments, water can obtain from the power station that off-gas stream also is provided.For example, in water-cooled power station such as cooled with seawater power station, can be sent to settling system then also as the water in the precipitin reaction for the used water in power station.In some these embodiment, described water can be through cooling before entering precipitation reactor.

In embodiment shown in Figure 1, at first filled with CO from the divalent cation solution in divalent cation source 110 ₂Charged into CO and produce ₂Water, this CO ₂Stand the carbonate cpds deposition condition then.As shown in fig. 1, contain CO ₂Gaseous stream 130 contact at settling step 120 places with the solution of divalent cation.The gaseous stream 130 that is provided contacts at settling step 120 places with the suitable solution that contains divalent cation and produces and charged into CO ₂Water.Charged into CO ₂Water for CO ₂The water of gas contact, wherein CO ₂Molecule produces for example carbonic acid, supercarbonate and carbonate ion with water molecules chemical combination.In this step water is inflated the " CO that causes water ₂Content " raising of (with for example form of carbonic acid, supercarbonate and carbonate ion) and the pCO of the waste streams that contacts with water ₂Reduce together.The described CO that charged into ₂Water may be tart, pH is 6 or lower, for example 5 or lower, comprise 4 or lower.In certain embodiments, be used for CO to the gas of water inflation ₂Concentration can be 10% or higher, 25% or higher, comprise 50% or higher, for example 75% or even higher.The contact method of being concerned about includes but not limited to: directly contact method (as to as described in the drum bubble of volume), following current route of exposure (being to contact between gas and the liquid phase stream of uniflux), adverse current approach (being to contact between gas and the liquid phase stream of reversed flow) etc.Therefore, contact can be according to conformance by using realizations such as injector, bubbler, fluid Venturi reactor, sparger, gas filter, spraying, column plate or packing tower reactor.

To be settled out at settling step 120 places and may be amorphous or crystalline carbonate cpds.The deposition condition of being concerned about comprises that the physical environment that changes water is to produce those of required sedimentable matter.For example, the temperature of water can be risen to the sedimentary amount that is suitable for taking place required carbonate cpds.In such embodiments, the temperature of water can be risen to 5-70 ℃ value, for example 20-50 ℃, comprise 25-45 ℃.Therefore, though the set of the deposition condition of giving can have 0-100 ℃ temperature range, but in certain embodiments elevated temperature to produce required sedimentable matter.In certain embodiments, the energy that temperature can be used from the source of low or zero Carbon emission such as solar energy source, wind energy, HYDROELECTRIC ENERGY etc. produce raises.Though the pH of water can be promoted to pH alkaline level to drive the precipitation of carbonate cpds in certain embodiments as required in the 7-14 scope in set precipitation process.In some these embodiment, pH can be promoted to and make CO in the precipitation process ₂The generation of gas minimizes the level of (if not the words of eliminating).In these embodiments, pH can be promoted to 10 or higher, for example 11 or higher.When needing, the pH of water can promote with any suitable method.Can adopt the pH-rising agent in certain embodiments, wherein the example of this class reagent comprises oxide compound, oxyhydroxide (as sodium hydroxide, potassium hydroxide, brucite), carbonate (as yellow soda ash) etc.The amount that is added to the pH-elevator in the salt water source should depend on the specific nature of reagent and the volume of reformed salt water, and should be enough to promote the pH in salt water source to required value.Perhaps, the pH in salt water source can be increased to desired level by the electrolysis of water.

CO ₂Charge into the precipitation of carbonate cpds can the successive process or separation steps carry out.Therefore, according to certain embodiments of the present invention, charge into and precipitate and can be as shown in fig. 1 in step 120 is in the same reactor of system, carry out.And in other embodiments of the present invention, these two steps can be carried out in independent reactor, so that water is filled with CO in inflation reactor (being solution-air or gas-liquid-solid contactor) earlier ₂, gained has charged into CO ₂Water in independent reactor, stand deposition condition then.

Behind the carbonato sedimentable matter of described water generates, can be as shown in fig. 1 (be gained CO at step 140 place with the gained sedimentable matter ₂Cut and deposit component) separate to produce isolating sedimentable matter with some or all mother liquors.The available any suitable method of the separation of sedimentable matter realizes, comprise mechanical means, for example wherein a large amount of excessive water are by for example gravity self or apply the vacuum machine extruding and discharge, produce filtrate etc. by filtering separation sedimentable matter and mother liquor from sedimentable matter.Be used for example system and the method that big water gaging is removed for available among the present invention, referring to the U.S. Provisional Patent Application of submitting on March 10th, 2,009 61/158,992,61/168 of submission on April 9th, 2009,166,61/170 of submission on April 16th, 2009,086,61/178 of submission on May 14th, 2009,475,61/228 of submission on July 24th, 2009,210,61/230 of submission on July 30th, 2009,61/239 of submission on September 2nd, 042 and 2009,429, it respectively is attached to herein by reference.It (is the dehydration CO of the concrete composition of carbon footprint minimizing that the separation of big water gaging will produce wet dehydration lees matter ₂Cut and deposit component).

Gained dehydration lees matter can directly be used, or gained dehydration lees matter can be through further drying.In some embodiments, gained dehydration lees matter can directly be used.Directly using gained dehydration lees matter may be suitable in the application of a certain amount of water of needs.In non-limiting instance, dehydration lees matter can be mixed with normal portland cement, wherein dehydration lees matter provides the aquation of cement admixture and builds required portion water at least.In some embodiments, dehydration lees matter can contain and surpass 5% water, surpass 10% water, surpasses 20% water, surpasses 30% water, surpasses 50% water, surpasses 60% water, surpasses 70% water, surpasses 80% water, surpass 90% water or surpass 95% water.In some embodiments, dehydration lees matter will provide at least 5% required water of the application of using this dehydration lees matter, at least 10% water, at least 20% water, at least 30% water, at least 40% water, at least 50% water, at least 60% water, at least 70% water, at least 80% water, at least 90% water or at least 95% water.In some embodiments, dehydration lees matter will provide the required whole water of application that use this dehydration lees matter.For example, dehydration lees matter can provide dehydration lees matter and normal portland cement cement admixture aquation and build required whole water.For example, sedimentable matter can be through dehydration so that dehydration lees matter comprises nearly 70% water, 66.5% water for example.The slurry of sedimentable matter can be mixed with normal portland cement then so that the gained cement admixture comprises 80% normal portland cement and 20% sedimentable matter, wherein the ratio of water and cement (being that normal portland cement adds sedimentable matter) is about 40%.The amount of the water that removes from sedimentable matter by control, the carbon footprint of the material that the autoprecipitation material makes (concrete that reduces as the carbon footprint) be also with controlled, if material require water especially.Consider this point, low, the neutral or negative carbon footprint of described any product material can be by only removing the water of the required amount that removes and further minimizing from sedimentable matter herein.

As mentioned above, gained dehydration lees matter also can be as drying shown in the step 160 among Fig. 1 to produce goods.Drying can realize by dry air filtrate.When filtrate during through dry air, dry air can be carried out under room temperature or high temperature.Dehydration lees matter can produce to contain and be lower than 50% water, is lower than 40% water, is lower than 30% water, is lower than 20% water, is lower than 10% water or is lower than the sedimentable matter of 5% water through dry air.For example, dehydration lees matter can produce through dry air and contains 30% or the sedimentable matter of still less water.Such sedimentable matter can with or without the situation of other processing (as high shear mixing) under crushing and comprise the aquation of cement admixture and build the cement admixture of required portion water with other materials such as normal portland cement combination results.Drying also can realize by the spraying drying sedimentable matter, the liquid that wherein contains sedimentable matter is dry by the hot gas (the off-gas stream of the spontaneous power plant of Tathagata) that flows through is provided, and for example wherein liquid feeding is pumped through spraying gun and enters in the main kiln and hot gas passes through as the following current or the adverse current of spraying gun direction.The specific drying means that depends on system, dry station can contain filtering element, lyophilize structure, spraying drying structure etc.

When needing, from liquid-solid isolating dehydration lees matter can as shown in the optional step 150 of Fig. 1 before dry through washing.Sedimentable matter can be with the fresh water washing for example to remove desalt (as NaCl) from dehydration lees matter.With after washing water can be disposed according to conformance, for example in tailing pond, dispose etc.

At step 170 place, the sedimentable matter of drying can choose wantonly through refining with for example obtain required physical properties such as particle diameter, surface-area etc. or in sedimentable matter, add one or more components such as admixture, aggregate, supplementary cementitious material etc. to produce end article 80.

Fig. 4,5 and 6 has provided preparation CO ₂Cut the synoptic diagram of other embodiments of the method for depositing goods.In Fig. 6, CO ₂The source is directly from power station stack gas.Stack gas can be dissolved in the seawater, thereby extract CO ₂, SO _XAnd NO _XGas is to give off uncontaminated air.When dissolving, CO ₂Be converted into carbonic acid and with seawater in divalent cation (as Ca ²⁺, Mg ²⁺) form carbonate and produce SCM and aggregate, NO simultaneously _XAnd SO _XAlso be neutralized and cut and deposit.Can form and the slurry of spraying drying carbonate containing (as lime carbonate and/or magnesiumcarbonate) to produce required particle diameter.Process comprises accurate control sodium-chlor (to avoid the corrosive nature to reinforcing bar) and generation uncontaminated air and can be easier to the clean water of desalination because of hardness reduction (concentration as calcium and magnesium reduces).Though it is undesirable that magnesium is regarded as in the concrete, this MgCO ₃Form is than the magnesium hydroxide of avoiding usually (Mg (OH) ₂) more be similar to CaCO ₃

In certain embodiments, can adopt the system 200 of system such as Fig. 2 to carry out aforesaid method.The system 200 of Fig. 2 comprises and contains CO ₂Gas source 230 (stack gas in Tathagata spontaneous combustion coal power station).This system also contains structure for conveying such as pipe, conduit or pipeline, and it will contain CO ₂Gas from containing CO ₂Gas source 230 guiding to treater 220.Also show the source of solvent 210 that contains divalent cation (as water body, contain the solution tank of divalent cation etc.) among Fig. 2.In some embodiments, the source of solvent 210 that contains divalent cation contains structure for conveying such as pipe, conduit or pipeline, and its solution (as the alkaline including earth metal ionic aqueous solution) guiding that will contain divalent cation is to treater (220).When the source of solvent that contains divalent cation was seawater, structure for conveying was communicated with (for example, be input as pipeline or feeding from seawater to land system, or be input as the inlet in the hull in the maritime system) with the source of seawater fluid.

The divalent cation aqueous solution that offers treater or its parts (as solution-air contactor, gas-liquid-solid contactor etc.) can be by recirculating pump recirculation so that contain CO ₂Gas (as comprise CO ₂, SO _X, NO _X, metal and metallic compound, particulate matter etc.) be absorbed in solution-air contactor in the treater or the gas-liquid-solid contactor and be optimized.When being with or without recirculation, treater of the present invention or its parts (as solution-air contactor, gas-liquid-solid contactor etc.) can realize containing CO ₂Gas at least 25%, 50%, 70% or 90% CO ₂Dissolving.Other gases are (as SO _X) dissolving may in addition higher, for example at least 95%, 98% or 99%.Provide and contain CO ₂Other parameters of optimal absorption of gas comprise 0.1-30,1-20,3-20 or 5-20cm ^-1Specific surface area; 0.05-2, the hydraulic fluid side mass transfer coefficient (KL) of 0.1-1,0.1-0.5 or 0.1-0.3cm/s; With 0.01-10,0.1-8,0.3-6 or 0.6-4.0s ^-1Volume transmission quality coefficient (K _LA).In some embodiments, the aqueous solution of divalent cation is to containing CO ₂The absorption of gas will make at least that the partly precipitated material precipitates in the solution-air contactor.In some embodiments, precipitation mainly takes place in the settling vessel of treater.Treater also can provide preliminary settlement measurement (being that treater can serve as slurry tank) when making the sedimentary structure of sedimentable matter providing.No matter whether provide sedimentation, treater all can provide the slurry of sedimentable matter to the dehydration feed pump, and the dehydration feed pump offers liquid-solid separator with the slurry of sedimentable matter again, and sedimentable matter will be separated at liquid-solid separator place with the precipitin reaction mixture.

Treater 220 can also contain any in a large amount of different parts, includes but not limited to the parts of thermoswitch (as being configured to the thermal precipitation reaction mixture to temperature required), chemical additive component (as removing chemical agent such as oxyhydroxide, metal oxide or flyash to introduce proton), electrochemistry parts (as cathode/anode), mechanical agitation and/or physical agitation mechanism and is used to make the parts of factory's stack gas recirculation by settler.Treater 220 can also contain the parts that are configured to monitor one or more parameters, and described parameter includes but not limited to reactor internal pressure, pH, sedimentable matter particle diameter, concentration of metal ions, conductivity, basicity and pCO ₂Treater 220 can with whole settler as one man with intermittent mode, semi-batch mode or operation continuously.

Treater 220 also contains and is used to comprise the slurry of sedimentable matter or the output transport unit of separated liquid supernatant.In some embodiments, the output transport unit is configurable to carry slurry or supernatant liquor to tailing pond (so that disposal) or naturally occurring water body Ru Yang, sea, lake or river.In other embodiments, system can be configured to by the pipeline between settling system and factory and makes described slurry or supernatant liquor can be used as the refrigerant of factory.In certain embodiments, settler can be arranged in same place with desalting plant, so that be used as the input water of desalting plant from the output water of settler.System can contain transport unit (as conduit), and via such transport unit, output water (as slurry or supernatant liquor) can directly be pumped in the desalting plant.

System shown in Fig. 2 also contains liquid-solid separator 240 so that sedimentable matter is separated from the precipitin reaction mixture.Liquid-solid separator can be realized the separation of sedimentable matter from the precipitin reaction mixture by draining (for example draining behind the gravity settling of sedimentable matter), decant, filtration (forcing air filtration as gravity filtration, vacuum filtration, use), centrifugal, extruding or its arbitrary combination.At least one liquid-solid separator effectively is connected with treater, but so that precipitin reaction mixture self processor flows to liquid-solid separator.Can arrange arbitrarily (as parallel, the series connection or its combination) use in combination in any many different liquid-solid separators, the precipitin reaction mixture can directly flow to liquid-solid separator or the precipitin reaction mixture can be through pre-treatment.

System 200 also contains washer (250), locates to obtain earlier washing (for example desalting and other solutes to remove) here before dry from sedimentable matter in drying station (for example moisture eliminator 260) from a large amount of dehydration lees matter of liquid-solid separator 240.

System can also contain the sedimentable matter that comprise carbonate (as lime carbonate, magnesiumcarbonate), supercarbonate or its combination of moisture eliminator 260 to produce in the drying treatment device.According to specific system, moisture eliminator can contain filtering element, lyophilize structure, spraying drying structure etc.System can contain the forwarder (as conduit) that connects factory and moisture eliminator and contain CO so that can make ₂Gas (as factory's stack gas) in drying stage, directly contact with wet sedimentable matter.

The sedimentable matter of drying can made with extra care 270 places, station through further processing (as grinding, milling) to obtain required physical properties.If sedimentable matter will can add one or more components as material of construction in sedimentable matter in treating process.

System also contains and is configured to remove the outlet forwarder (as travelling belt, shurry pump) of sedimentable matter from following one or more: treater, moisture eliminator, washer or refining station.As mentioned above, sedimentable matter can different ways be disposed.Can in the carrier vehicle (as barge, railway carriage, truck etc.) of sky sedimentable matter be transported to the long storage point, long storage point can comprise on the ground and underground installation.In other embodiments, sedimentable matter is disposed in the position under water.Sedimentable matter can be transported to any suitable transfer structure of disposing point all can adopt.In certain embodiments, can adopt pipeline or similar slurry transfer structure, wherein these structures can contain the unit that is used for initiatively pumping, gravity induced flow etc.

Those skilled in the art should be familiar with, and the flow rate of described system and method, mass transfer and heat transfer herein can be different and can be optimized, and the parasitic load in power station can reduce and simultaneously carbon cut to deposit and obtain maximization.

The solidifiable composition

Other aspects of the present invention relate to the solidifiable composition of the combination that contains concrete composition that carbon footprint of the present invention reduces and water.Solidifiable composition of the present invention can be by merging concrete composition and water or by merging concrete and aggregate in advance, merging that gained is done component and water produces then simultaneously.

Dried component can merge with it and produce solidifiable composition such as concrete liquid phase such as aqueous fluid can differently also can be pure water or the water that contains one or more solutes, additive, cosolvent etc. as required.The ratio of doing the liquid phase that is merged in component and the solidifiable preparation of compositions can be different, in certain embodiments 2: 10-7: in 10 scopes, for example 3: 10-6: 10, comprise 4: 10-6: 10.

Current cement standard such as ASTM C150 allow in portland cement is made with razor stone lime stone instead of part grog.Under ASTM C150 situation, maximum permission percentage ratio is 5%.In some European standards, in the preparation portland cement, want high as the permission percentage ratio of the substitute of grog with Wingdale, often be 10% but sometimes up to 30%.In these cases, Wingdale can be levigate separately and with the portland cement mix, but limestone aggregate also can be added in the grog and with grog and a small amount of gypsum in the ball milling stage and grinds the generation portland cement mutually.

Cut the calcium carbonate additive of depositing precipitin reaction and the use of the Wingdale of non-natural extraction has some benefits to the cement producer from carbon.Suppose to replace 5% grog with described sedimentable matter, then the concrete carbon footprint of gained can reduce 7.2%, and when using the razor stone lime stone, and the carbon footprint can only reduce 5% or still less.Consider the pressure of the minimizing carbon footprint that portland cement industry faces, have sizable value than this carbon footprint of 2.2% of the Wingdale that the uses extraction minimizing of Duo.

The Wingdale than extraction is purer usually to use precipitated chalk to be it as another benefit of grog substitute.In many cases, because of the character of impurity reduction gained portland cement, so the impurity in the Wingdale will limit the consumption of this Wingdale to being lower than maximum permission amount.In some portland cement factory, the capabilities limits of Wingdale of using local extraction is in perhaps 2.0%.Amount with 5% adopts carbon to cut and deposits the improvement that precipitated chalk will bring carbon footprint minimizing 5.2% (2.0% to 7.2%).

Use carbon to cut to deposit the minimizing of the portland cement carbon footprint that precipitated chalk brings also to have because of carbon credit (carbon credit) and produces the additional benefit of taking in potentially.Because add the amount that material (even if it is the Wingdale of extraction) will reduce the grog that uses, obtain the possible of carbon credit so have because of the cement mill reduces discharging.Cut the CO that deposits in the sedimentable matter ₂Can be used for improving amount and the value that reduces available carbon credit because of grog.

Practicality

Concrete of the present invention and contain concrete solidifiable composition of the present invention and can be used in the multiple different application is particularly as building or structured material.The ad hoc structure that solidifiable composition of the present invention can be used for includes but not limited to: the foothold on road surface, building structure (as buildings, ground, motorway/road, viaduct, parking lot, brick/piece wall) and door, fence and column, bridge, ground, dike, dam.Mortar of the present invention can be used for structure building block such as brick lumping together and the gap of interstitital texture blockhouse.Mortar also can be used to repair existing structure, for example to replace the purposes such as part that wherein original mortar is in damaged condition or lost.

Embodiment of the present invention can be used for reducing construction of buildings and use the CO that generates in the buildings then ₂Amount.Particularly, method of the present invention can reduce CO in material of construction such as the concrete production ₂Generation.In addition, method of the present invention can reduce CO in the generating ₂Discharging, this will reduce in its time limit of service and use the relevant CO of buildings ₂Discharging.

Method and system of the present invention can be used for CO ₂Cut and deposit, particularly exist in the architectural environment by cutting.Cut and deposit CO ₂Comprising drifts from gaseous stream such as off-gas removes or isolates CO ₂And be fixed in the stable non-gaseous so that CO ₂Can not escape in the atmosphere.CO ₂Cutting bag deposit draws together CO ₂Place the form of shelf-stable, for example the parts of architectural environment such as buildings, road, dam, dike, ground etc.Therefore, the CO of the method according to this invention ₂Cut and deposit and to prevent CO ₂Gas enters atmosphere and with CO ₂Do not become the mode long storage CO of an atmospheric part ₂The form of shelf-stable refer to can be under the condition that exposes (promptly being exposed to atmosphere, groundwater environment etc.) be stored on the ground or reach under water the long period as 1 year or longer, 5 years or longer, 10 years or longer, 25 years or longer, 50 years or longer, 100 years or longer, 250 years or longer, 1000 years or longer, 10,000 year or longer, 1,000,000 year or longer or even 100,000,000 year or longer and do not have the material form of significant (if any) degraded.Along with a little (if any) degraded takes place in the form of shelf-stable in storage process, the CO that discharges with own product ₂The amount of the degraded that gas is measured (if any) will be no more than for 5%/year, will be no more than for 1%/year in certain embodiments.On the ground the form of shelf-stable can be various envrionment conditions as the humidity of-100 ℃ to 600 ℃ temperature, 0-100% under shelf-stable, wherein said condition can be gentle, windy, violent or windy sudden and violent.Similarly, the stable form of underwater storage is to underwater environment conditional stability.The embodiment of method of the present invention can be used to catch all useless CO of commercial run such as generating, manufacture of cement, chemical production, papermaking and steel mill etc. ₂

The following examples are for providing to those skilled in the art about how realizing and use complete disclosure and description of the present invention to provide, but not are intended to limit the scope of the invention or be intended to represent that following embodiment is all or the unique experiment of being carried out.Endeavour to ensure the accuracy of used numerical value (as amount, temperature etc.), but should be taken into account certain experimental error and deviation.

It is the notion that development proposed that promotes this area that all embodiment that mention herein and conditional language mainly are intended to help the reader understanding's principle of the present invention and the inventor, and is interpreted as being not limited to embodiment and the condition that this class is specifically mentioned.In addition, mention herein principle of the present invention, aspect and embodiment with and all statements of specific examples be intended to contain its 26S Proteasome Structure and Function Equivalent.In addition, this class Equivalent is intended to comprise that the Equivalent of present known Equivalent and future development promptly develops any element of the realization identical function that and tubular construction is not how.Therefore scope of the present invention is not limited to illustrated and described exemplary herein, because this class embodiment only provides as an example.Really, those skilled in the art may expect numerical value change, change and substitute and do not depart from scope of the present invention.Below the claim method and structure and the Equivalent thereof that are intended to limit in the scope of scope of the present invention and these claims contain thus.

Embodiment

I. the component of the concrete composition that reduces of carbon footprint

A. auxiliary gelling mineral additive (SCMA)

Auxiliary gelling mineral additive (SCMA) is the partially or completely surrogate of conventional SCMs, its can with the portland cement mix with the concrete carbon footprint of remarkable minimizing, improve concrete quality, intensity and weather resistance simultaneously.SCMA is reactive admixture, and the cement of its alternative large volume or flyash increase weather resistance and do not have for example problem of early strength loss.SCMA can prepare described in U.S. Patent application 12/126,776 and U.S. Provisional Patent Application 61/088,347 and 61/101,626; It respectively is attached to herein by reference.

i.FTIR

FTIR uses laser excitation and measures the vibration of key in the material.Make in this way and can understand the compound that exists in the material.Normal portland cement slurry (OPC) has been shown among Fig. 7 and contain 20% SCMA and the mixed pulp of 80% OPC between the not comparison of aquation and aquation (in the time of 7 days).Though be not quite similar, SCMA can be the basis and the member of many goods and the basic chemical constitution of representing all goods.In last figure, be centered close to 1450cm ^-1Big carrying means a large amount of existence of carbonate among the SCMA.3694cm ^-1And 2513cm ^-1The peak at place has shown the aquation of SCMA.Mix SCMA for aquation can see 858cm ^-1The peak at place reduces 872cm ^-1It is sharp that the peak at place becomes, and 712cm ^-1The gradient at place also becomes sharp.These vibration modes positions conform to the formation of calcite.In cement admixture, 2342cm above-mentioned ^-1The peak at place no longer exists, and expection was with situation about taking place when this was goods rehydration.Existence is corresponding to Mg (OH) ₂OH stretching vibration peak (3694cm ^-1), but compare Ca (OH) with the aquation of OPC ₂Formation (3644cm ^-1The peak at place) seems to be suppressed.For the OPC of aquation, because the carbonization of cement, so can be at 1481cm ^-1And 1426cm ^-1The place observes tangible CO ₃ ^2-Vibration modes.Ca (OH) ₂At 3644cm ^-1The place has big peak, and it is also corresponding to the OH stretching vibration.

ii.XRD

XRD comes the reflection of working sample with different scattered through angles X-bundle of rays.Reflection will be returned fingerprint and can discern specific compound.Can do a large amount of the observation to aquation OPC and mix SCMA from XRD (referring to Fig. 8 and Fig. 9):

All there are ettringite and portlandite among OPC and the mix SCMA.

Have calcite among the SCMA, and the amount of formed portlandite significantly reduces by 20%.

After 7 days, SCMA shows a little or does not have the sign of rock salt (NaCl) or brucite, and this satisfies ACI 318 standards about sodium-chlor control.

SCMA provides the evidence that the Mg in the calcite exhausts.

Calucium Silicate powder among the SCMA seems also to consume comparatively fast mutually.

The iii.SEM image

SEM image (Figure 10) shows that aquation OPC all has the form similar to acicular calcium aluminite and form C-S-H on cement particle surface with mix SCMA slurry.

Iv.X-ray fluorescence spectra (XRF)

Oxide compound	CaO	SiO ₂	Al ₂O ₃	Fe ₂O ₃	SO ₃	Na ₂O	MgO	Cl	K ₂O
										Content (% weight)	8.96	1.76	0.63	0.265	0.17	2.56	31.17	1.15	0.12
Element (% weight)	6.404	0.823	0.334	0.185	0.068	11.37	18.79	1.15	0.100

Table 1: the XRF ultimate analysis of SCM of the present invention

V. particle size analysis (PSA)

The particle size analysis of SCM of the present invention shows that median particle diameter is that 10.86361 microns, median size are 11.26930 microns.

Vi.SCMA is reactive

As shown in Figure 11, SCMA is reactive.

The vii.SCM form

Figure 12 has provided the SCM form.

B. subtract carbon admixt (CRA)

CRA not only is a mineral additive but also be fine aggregate, and its particle diameter and sand are similar.CRA is with CO ₂Cut and to exist in the concrete and give the planner by instead of part in the compound design or whole fine aggregates and cement is not done any substituting and promptly create neutral carbon or the concrete potential of carbon negativity.CRA is by the method production of describing in the U.S. Provisional Patent Application 61/056,972; It openly is attached to herein by reference.

C. coarse aggregate (AGG)

Coarse aggregate (AGG) can replace the part or all of common coarse aggregate in the compound.AGG makes the planner can be not do any substituting to cement and promptly creates neutral carbon or carbon negative concrete and keep concrete intensity.AGG CRA presses the method production of describing in the U.S. Provisional Application 61/056,972; It openly is attached to herein by reference.

D. from the sedimentable matter of seawater

Stir seawater (900 gallons) and by blasting the air-flow acidifying that 55scfm contains 10% carbonic acid gas (all the other are air) through being positioned at 1000 gallons of gaseous diffusers of adding a cover the plastic channel bottom.Monitoring pH is when pH stops gaseous diffusion when about pH8 reduces to pH5.5-6.In the seawater that is stirring through acidifying, add the magnesium hydroxide from the industrial tailings pond (1g/L) that contains some calcites and silicon-dioxide; PH rises to about pH8.Restart gaseous diffusion, reduce to pH7, stop air-flow thereafter until pH.

Slurry form with 10% adds the 22kg magnesium hydroxide with the dosage that increases progressively altogether by following repetitive mode in described acid seawater: add the magnesium hydroxide slurry and increase to pH8 until pH in the seawater that is stirring.Restart the gas delivery that contains 10% carbonic acid gas and return pH7 until the pH of the seawater that is stirring.Stop gas delivery, add slurry and return pH8 until pH.After having consumed the 22kg magnesium hydroxide, the diffusion of the gas by containing 10% carbonic acid gas makes the pH of the seawater that is stirring reduce to pH 7, stops gas delivery thereafter.The NaOH (aqueous solution) that adds about 43kg 50% (w/w) in the seawater that is stirring reaches pH10.15 until the pH of seawater.The gained sedimentable matter separates under gravity, filters then to separate with supernatant liquor.Filter cake is in 110 ℃ of oven dryings, ball millings then.

Sedimentable matter characterizes

X-ray fluorescence spectrometry (XRF) data (table 2) show that sedimentable matter mainly is made up of magnesiumcarbonate and lime carbonate.

	Na	Mg	Al	Si	S	Cl	K	Ca	Fe
										% weight	1.86	19.48	0.28	0.71	0.07	1.36	0.13	8.10	0.20

Table 2: the XRF ultimate analysis of sedimentable matter

	％CO ₂
		% weight	49.63

Table 3:CO ₂Percentage composition (coulometry)

X-ray diffraction of sedimentable matter (XRD) and thermogravimetric analysis (TGA/DTG) show and have hydromagnesite and aragonite (CaCO ₃) as main phase, rock salt (NaCl) as minor component.The XRD of sedimentable matter and the standard of hydromagnesite, aragonite and hydromagnesite are compared.TGA/DTG is at 257 ℃ and 412 ℃ flex point/peaks of locating to provide the indication hydromagnesite, and TGA/DTG is at 707 ℃ of flex point/peaks of locating to provide the indication aragonite.This result has also obtained the confirmation (infrared spectra is used for being each generation constitutional diagram in aragonite, hydromagnesite and the sedimentable matter) of infrared spectra (IR).Such sedimentable matter can be used for producing the concrete composition that carbon footprint of the present invention reduces.

E. from the sedimentable matter of seawater

Stir seawater (900 gallons) and by blasting the air-flow acidifying that 55scfm contains 10% carbonic acid gas (all the other are air) through being positioned at 1000 gallons of gaseous diffusers of adding a cover the plastic channel bottom.Monitoring pH is when pH stops gaseous diffusion when about pH8 reduces to pH5.5-6.In the seawater that is stirring through acidifying, add magnesium hydroxide (1g/L); PH rises to about pH8.Restart gaseous diffusion, reduce to pH7, stop air-flow thereafter until pH.The NaOH (aqueous solution) that in the described seawater that is stirring, adds 30kg 50% (w/w) then with the dosage that increases progressively by following repetitive mode altogether: in the seawater that is stirring, add NaOH and increase to pH8 until pH.Restart the gas delivery that contains 10% carbonic acid gas and return pH7 until the pH of the seawater that is stirring.Stop gas delivery, add NaOH and return pH8 until pH.Behind the NaOH that has consumed 30kg 50% (w/w) (aqueous solution), the diffusion of the gas by containing 10% carbonic acid gas makes the pH of the seawater that is stirring reduce to pH7, stops gas delivery thereafter.The NaOH (aqueous solution) that adds about 37kg50% (w/w) in the seawater that is stirring reaches pH10.15 until the pH of seawater.The gained sedimentable matter separates under gravity, filters then to separate with supernatant liquor.Filter cake slurryization again in fresh water, spraying drying, ball milling then.

Sedimentable matter characterizes

X-ray fluorescence spectrometry (XRF) data (table 4) show that sedimentable matter mainly is made up of magnesiumcarbonate and lime carbonate.

	Na	Mg	Al	Si	S	Cl	K	Ca	Fe
										% weight	7.13	13.84	0.10	0.11	0.17	4.75	0.17	5.63	0.03

Table 4: the XRF ultimate analysis of sedimentable matter

	％CO ₂
		% weight	53.60

Table 5:CO ₂Percentage composition (coulometry)

X-ray diffraction of sedimentable matter (XRD) and thermogravimetric analysis (TGA/DTG) show and have nesquehonite (MgCO ₃3H ₂O) and aragonite (CaCO ₃) as main phase, rock salt (NaCl) as minor component.The XRD of sedimentable matter and the standard of nesquehonite and aragonite are compared.TGA/DTG is at 132 ℃, 364 ℃, 393 ℃ and 433 ℃ flex point/peaks of locating to provide the indication nesquehonite, and TGA/DTG is at 697 ℃ of flex point/peaks of locating to provide the indication aragonite.This result has also obtained the confirmation (infrared spectra is used for being each generation constitutional diagram in nesquehonite, aragonite and the sedimentable matter) of infrared spectra (IR).Such sedimentable matter can be used for producing the concrete composition that carbon footprint of the present invention reduces.

Sedimentable matter from seawater

In 200,000 gallons open containers, mix seawater (76,000 gallons), way be with two its contents of pump pumping through two pipelines and with the circular trace that makes progress with in the described content return slot.Spread carbon dioxide (100%) to reduce pH by the scatterer that is arranged in bottom land to seawater to about pH5.5.About 800kg magnesium hydroxide from tailing pond that will contain some calcites and silicon-dioxide injects described open containers with the seawater slurryization and on this operation prerequisite basis of pond sand filter by recirculation device.After adding magnesium hydroxide, stop the conveying of 100% carbon dioxide.Adding causticity (50% (w/w)) NaOH (aqueous solution) by recirculation line then is pH9.5 until the pH of slurry.Then slurry is transferred to settling bowl, decant removes supernatant liquor and collects the gravity settling solid to carry out spraying drying.Collect with the slurry spraying drying and from the main chamber of spray-dryer.

Sedimentable matter characterizes

X-ray fluorescence spectrometry (XRF) data (not shown) shows that sedimentable matter mainly is made up of magnesiumcarbonate and lime carbonate.

	％CO ₂
		% weight	33.06

Table 6:CO ₂Percentage composition (coulometry)

X-ray diffraction of sedimentable matter (XRD) and thermogravimetric analysis (TGA/DTG) show and have nesquehonite (MgCO ₃3H ₂O) and single hydroconite (CaCO ₃H ₂O) as main phase, aragonite (CaCO ₃) and rock salt (NaCl) as minor component.The XRD of sedimentable matter and the standard of nesquehonite, aragonite and single hydroconite are compared.TGA/DTG is at 136 ℃, 187 ℃ and 421 ℃ flex point/peaks of locating to provide the indication nesquehonite, and TGA/DTG is at 771 ℃ of flex point/peaks of locating to provide indication aragonite and single hydroconite.This result has also obtained the confirmation (infrared spectra is used for being each generation constitutional diagram in nesquehonite, aragonite, single hydroconite and the sedimentable matter) of infrared spectra (IR).Such sedimentable matter can be used for producing the concrete composition that carbon footprint of the present invention reduces.

II. carbon footprint contrast

Compound design for reducing corresponding carbon footprint below because of using goods of the present invention to expect.Concrete carbon footprint is by taking advantage of its every pound carbon footprint, these value summations being added 10.560kg/yd again with every cubic yard of poundage of each constituent element ³(1 yard concrete transports 20 miles average carbon footprint) calculates.

The transportation footprint:

The numeral that European Commission has issued by truck transport (aggregate, cement and concrete) is 160g CO ₂/ metric ton material/km.Cement has been estimated as 0.150 pound of CO through the carbon footprint of sea route from the Asia shipping to California ₂Every pound of sea-freight thing.

Suppose that with the mean distance of 50 miles of aggregate carryings and the carbon footprint of supposition generation be 0.03 pound of CO ₂/ pound aggregate, then the average carbon footprint of aggregate is about 0.043 pound of CO ₂/ pound aggregate.

Flyash and slag transport the carbon footprint that passes through whole state in the railway mode and have been estimated as only 0.020 pound of every pound of flyash.Suppose that flyash or slag transport average 100 miles in the lorry mode, then the carbon footprint of conventional SCMs will be about 0.045 pound of CO ₂/ pound flyash or slag.

Produce footprint:

Suppose the average CO that produces from portland cement ₂Burst size is 0.86 tonne of CO ₂/ metric ton cement (according to California Cement Climate Action Team's), then the carbon footprint of the production of every pound of portland cement is 0.86 pound.The assumed average shipment distance is 100 miles, and the transportation footprint of every pound of portland cement is 0.016 pound, so the total carbon footprint of every pound of portland cement is 0.876 pound of CO ₂

Subtract the carbon amount:

Material such as SCMA, CRA and AGG cut the CO that deposits ₂Content approximately slightly 50%, its correspondence-0.500 pound CO ₂The carbon footprint of every pound of material.The carbon footprint of producing and transporting (supposition is transported average 100 miles distance in the lorry mode) is about 0.050 pound of CO ₂Every pound of material.Therefore total carbon footprint is-0.450 pound of CO ₂Every pound of material.

A.100%OPC compound

Composition	Pound CO ₂/ pound composition	Pound composition/yd ³Concrete	Pound CO ₂/yd ³Concrete
				Portland cement	0.876	564	494.06
Water	0.01	282	2.82
				Flyash	0.045	0	0
SCMA	(0.450)	0	0
				Fine aggregate	0.043	1,300	55.90
CRA	(0.450)	0	0

Coarse aggregate	0.043	1,800	77.40
				AGG	(0.450)	0	0
Amount to		3,946	630.18

Table 7: the carbon footprint is 630.18 pounds of CO ₂/ yd ³Concrete concrete composition

The carbon footprint of this typical 6-bag concrete compound embodiment is 630 pounds every cubic yard.To alleviate this carbon emission with biological mode and need plant one foot of diameter, high 27 feet tree.Per 10 yards loads are amounted to the hurst of 10 such trees of plantation!

B. high fly-ash (50%) compound

Composition	Pound CO ₂/ pound composition	Pound composition/yd ³Concrete	Pound CO ₂/yd ³Concrete
				Portland cement	0.876	282	247.03
Water	0.01	282	2.82
				Flyash	0.045	282	12.69
SCMA	(0.450)	0	0
				Fine aggregate	0.043	1,300	55.90
CRA	(0.450)	0	0
				Coarse aggregate	0.043	1,800	77.40
AGG	(0.450)	0	0
				Amount to		3,946	395.84

Table 8: the carbon footprint is 395.84 pounds of CO ₂/ yd ³Concrete concrete composition

The 50% carbon footprint that substitutes with this typical 6-bag concrete compound embodiment of flyash is 395 pounds every cubic yard, reduces 37% than the carbon footprint of direct 6-bag portland cement compound.

What C. have improved serviceability subtracts the carbon compound

Composition	Pound CO ₂/ pound composition	Pound composition/yd ³Concrete	Pound CO ₂/yd ³Concrete
				Portland cement	0.876	338	296.09
Water	0.01	282	2.82

Flyash	0.045	113	5.08
				SCMA	(0.450)	113	(50.85)
Fine aggregate	0.043	1,300	55.90
				CRA	(0.450)	0	0
Coarse aggregate	0.043	1,800	77.40
				AGG	(0.450)	0	0
Amount to		3,946	386.44

Table 9: the carbon footprint is 386.44 pounds of CO ₂/ yd ³Concrete concrete composition

The carbon footprint of this typical 6-bag concrete compound embodiment that contains the OPC of 20% SCMA, 20% flyash and 60% is 386 pounds every cubic yard, lacks 2% than the carbon footprint of the compound of 50%OPC/50% flyash.This compound will obtain less carbon footprint and not have the time of coagulation and the early strength problem of 50% coal ash mixed material, as shown in Figure 3.

D. the neutral carbon compound that contains 6 bags of OPC

Composition	Pound CO ₂/ pound composition	Pound composition/yd ³Concrete	Pound CO ₂/yd ³Concrete
				Portland cement	0.876	564	494.06
Water	0.01	282	2.82
				Flyash	0.045	0	0
SCMA	(0.450)	0	0
				Fine aggregate	0.043	1,300	55.90
CRA	(0.450)	1,400	(630.00)
				Coarse aggregate	0.043	1,700	73.10
AGG	(0.450)	0	0
				Amount to		3,946	(4.12)

Table 10: the carbon footprint is 494.06 pounds of CO ₂/ yd ³Concrete concrete composition

The 6-bag concrete compound embodiment of this neutral carbon uses CRA to substitute the parts of fine aggregate.

E.OPC is by a large amount of neutral carbon compounds that substitute and have improved processing characteristics

Composition	Pound CO ₂/ pound composition	Pound composition/yd ³Concrete	Pound CO ₂/yd ³Concrete
				Portland cement	0.876	338	296.09
Water	0.01	282	2.82
				Flyash	0.045	113	5.08
SCMA	(0.450)	113	(50.85)
				Fine aggregate	0.043	600	25.50
CRA	(0.450)	800	(360)
				Coarse aggregate	0.043	1,800	77.40
AGG	(0.450)	0	0
				Amount to		3,946	(3.96)

Table 11: the carbon footprint is-3.96 pounds of CO ₂/ yd ³Concrete concrete composition

The 6-bag concrete compound embodiment of this neutral carbon uses CRA to substitute the parts of fine aggregate, and has used SCMA and flyash, and alternative level respectively is 20%.

Other compounds of being concerned about comprise:

Composition	Pound CO ₂/ pound composition	Pound composition/yd ³Concrete	Pound CO ₂/yd ³Concrete
				Portland cement	0.876	338	296.1
Water	0.01	271	2.7
				Fine aggregate	0.013	1,250	16.3
Coarse aggregate	0.013	1,800	23.4
				Flyash	0.045	113	5.1
CM-SCM	(0.450)	113	(50.9)
				Carefully-SA	0	0	0
Slightly-SA	0	0	0
				Amount to		3,885	293

Table 12: the carbon footprint is 293 pounds of CO ₂/ yd ³Concrete concrete composition

Composition	Pound CO ₂/ pound composition	Pound composition/yd ³Concrete	Pound CO ₂/yd ³Concrete
				Portland cement	0.876	451	395.1
Water	0.01	282	2.8
				Fine aggregate	0.013	1250	16.3
Coarse aggregate	0.013	1,800	23.4
				Flyash	0	0	0
CM-SCM	(0.450)	113	(50.9)
				Carefully-SA	0	0	0
Slightly-SA	0	0	0
				Amount to		3,896	386.7

Table 13: the carbon footprint is 386.7 pounds of CO ₂/ yd ³Concrete concrete composition

Composition	Pound CO ₂/ pound composition	Pound composition/yd ³Concrete	Pound CO ₂/yd ³Concrete
				Portland cement	0.876	338	296.1
Water	0.01	271	2.7
				Fine aggregate	0.013	616	8.0
Coarse aggregate	0.013	1,800	23.4
				Flyash	0.045	113	5.1
CM-SCM	(0.450)	113	(50.9)
				Carefully-SA	(0.450)	634	(285.3)
Slightly-SA	(0.450)	0	0
				Amount to		3,885	(0.9)

Table 14: the carbon footprint is-0.9 pound of CO ₂/ yd ³Concrete concrete composition

Composition	Pound CO ₂/ pound composition	Pound composition/yd ³Concrete	Pound CO ₂/yd ³Concrete
				Portland cement	0.876	564	494.1
Water	0.01	282	2.8
				Fine aggregate	0.013	138	1.8
Coarse aggregate	0.013	1,800	23.4
				Flyash	0.045	0	0
CM-SCM	(0.450)	0	0
				Carefully-SA	(0.450)	1,162	(522.9)
Slightly-SA	(0.450)	0	0
				Amount to		3,946	(0.8)

Table 15: the carbon footprint is-0.8 pound of CO ₂/ yd ³Concrete concrete composition

F. high-carbon is caught compound

Composition	Pound CO ₂/ pound composition	Pound composition/yd ³Concrete	Pound CO ₂/yd ³Concrete
				Portland cement	0.876	338	269.09
Water	0.01	282	2.82
				Flyash	0.045	113	5.08
SCMA	(0.450)	113	(50.85)
				Fine aggregate	0.043	0	0
CRA	(0.450)	1,300	(585.00)
				Coarse aggregate	0.043	0	0
AGG	(0.450)	1,800	(810.00)
				Amount to		3,946	(1,168.86)

Table 16: the carbon footprint is-1,168.86 pounds of CO ₂/ yd ³Concrete concrete composition

This carbon cuts the material of depositing concrete the application of the invention and uses SCMA and flyash as the surrogate of coarse aggregate and fine aggregate and each with 20% alternative level and show high-carbon and catch concrete potentiality.The load of per 10 yards these compounds is equivalent to 1 foot of 19 diameter of plantation, high 27 feet tree!

The high-carbon that provides other is below caught prescription:

Composition	Pound CO ₂/ pound composition	Pound composition/yd concrete	Pound CO ₂/ yd concrete
				Portland cement	0.876	338	269.09
Water	0.01	271	2.71
				Flyash	0.045	113	5.09
SCMA	(0.450)	113	(50.85)
				Fine aggregate	0.043	0	0
CRA	(0.450)	1,250	(562.50)
				Coarse aggregate	0.043	0	0
AGG	(0.450)	1,800	(810.00)
				Amount to		3,885	(1,119.47)

Table 17: the carbon footprint is-1,119.47 pounds of CO ₂/ yd ³Concrete concrete composition

Composition	Pound CO ₂/ pound composition	Pound composition/yd ³Concrete	Pound CO ₂/yd ³Concrete
				Portland cement	0.876	338	269.1
Water	0.01	271	2.7
				Fine aggregate	0.013	0	0
Coarse aggregate	0.013	0	0
				Flyash	0.045	113	5.1
CM-SCM	(0.450)	113	(50.9)
				Carefully-SA	(0.450)	1,250	(562.5)
Slightly-SA	(0.450)	1,800	(810.0)
				Amount to		3,885	(1,146)

Table 18: the carbon footprint is-1,146 pounds of CO ₂/ yd ³Concrete concrete composition

Composition	Pound composition/yd composition	Pound CO ₂/ pound composition	Pound CO ₂/ yd concrete
				Portland cement	338	0.88	270
Water	282	0.01	3
				Fine aggregate	0	0.04	0
Coarse aggregate	0	0.04	0
				Flyash	113	0.045	5
SCM	113	(0.45)	(51)
				CRA	1,250	(0.45)	(563)
AGG	1,800	(0.45)	(810)
				Amount to	3,885		(1,145)

Table 19: the carbon footprint is 1,145 pound of CO ₂/ yd ³Concrete concrete composition

Though the front has slightly described the present invention for clear understanding purpose of the present invention in detail by signal and example, but it is evident that those skilled in the art can open do some change and modification and not depart from the spirit or scope of subsidiary claims it by of the present invention.

Therefore, the content of front has only been illustrated principle of the present invention.Though should be understood that those skilled in the art can find out does not variously clearly describe herein or illustrates but embody principle of the present invention and be included in scheme in its spirit and scope.In addition, it is the notion that development proposed that promotes this area that all embodiment that mention herein and conditional language mainly are intended to help the reader understanding's principle of the present invention and the inventor, and is interpreted as being not limited to embodiment and the condition that this class is specifically mentioned.In addition, mention herein principle of the present invention, aspect and embodiment with and all statements of specific examples be intended to contain its 26S Proteasome Structure and Function Equivalent.In addition, this class Equivalent is intended to comprise that the Equivalent of present known Equivalent and future development promptly develops any element of the realization identical function that and tubular construction is not how.Therefore scope of the present invention is not limited to illustrated and described exemplary herein.On the contrary, scope and spirit of the present invention are embodied by subsidiary claims.

Claims

1. method, described method comprises:

A) solution of self-contained divalent cation and comprise CO ₂Industrial gaseous waste produce the synthetic CARBONATE COMPONENT and

B) introduce described synthetic CARBONATE COMPONENT in the concrete composition that the carbon footprint reduces, the concrete composition that wherein said carbon footprint reduces has the carbon footprint of minimizing with respect to the normal concrete composition.

2. the process of claim 1 wherein that concrete composition that described carbon footprint reduces lacks than the carbon footprint of normal concrete composition.

3. the method for claim 2, the carbon footprint that the concrete composition that wherein said carbon footprint reduces has is lower than 75% of normal concrete composition.

4. the method for claim 3, the carbon footprint that the concrete composition that wherein said carbon footprint reduces has is lower than 50% of normal concrete composition.

5. the method for claim 3, the carbon footprint that the concrete composition that wherein said carbon footprint reduces has is lower than 25% of normal concrete composition.

6. the process of claim 1 wherein that the concrete composition that described carbon footprint reduces has the carbon neutral footprint.

7. the process of claim 1 wherein that the concrete composition that described carbon footprint reduces has negative carbon footprint.

8. according to the method for claim 6 or 7, the minimizing of the carbon footprint of the concrete composition that wherein said carbon footprint reduces is that carbonic acid gas is cut and deposits the result who is avoided with carbonic acid gas.

9.7 method, wherein said negative carbon footprint is lower than 0 pound of CO ₂/ yd ³The concrete composition that described carbon footprint reduces.

10.7 method, wherein said negative carbon footprint is lower than 250 pounds of CO ₂/ yd ³The concrete composition that described carbon footprint reduces.

11.7 method, wherein said negative carbon footprint is lower than 500 pounds of CO ₂/ yd ³The concrete composition that described carbon footprint reduces.

12.7 method, wherein said negative carbon footprint is lower than 1000 pounds of CO ₂/ yd ³The concrete composition that described carbon footprint reduces.

13. the process of claim 1 wherein that described synthetic CARBONATE COMPONENT is supplementary cementitious material, fine aggregate, coarse aggregate or active pozzolans material.

14. the method for claim 13, wherein said synthetic CARBONATE COMPONENT are aragonite, nesquehonite, hydromagnesite, single hydroconite or its combination.

15. the method for claim 14, wherein said synthetic CARBONATE COMPONENT are the combination of aragonite and hydromagnesite.

16. the method for claim 14, wherein said synthetic CARBONATE COMPONENT are the combination of aragonite and nesquehonite.

17. the method for claim 14, wherein said synthetic CARBONATE COMPONENT are the combination of nesquehonite and single hydroconite.

18. the method for claim 14, the δ of wherein said synthetic CARBONATE COMPONENT ¹³C is lower than-10 ‰.

19. the method for claim 14, the δ of wherein said synthetic CARBONATE COMPONENT ¹³C is lower than-20 ‰.

20. the method for claim 14, the δ of wherein said synthetic CARBONATE COMPONENT ¹³C is lower than-30 ‰.

21. composition that the carbon footprint that produces by the method for claim 1 reduces.

22. a composition, described composition comprise the calcium of 2.5%-50%, the magnesium of 2.5%-50% and at least 25% carbonate, supercarbonate or its mixture.

23. the composition of claim 22, wherein said composition comprises the calcium of 2.5%-25%.

24. the composition of claim 23, wherein said composition comprises the calcium of 5%-10%.

25. the composition of claim 22, wherein said composition comprises the magnesium of 5%-30%.

26. the composition of claim 25, wherein said composition comprises the magnesium of 10%-30%.

27. the composition of claim 22, wherein said composition comprise at least 50% carbonate, supercarbonate or its mixture.

28. the composition of claim 27, wherein said composition comprise at least 75% carbonate, supercarbonate or its mixture.

29. the composition of claim 22, wherein said composition comprise aragonite, nesquehonite, hydromagnesite, single hydroconite or its combination.

30. the composition of claim 29, wherein said composition comprises the combination of aragonite and hydromagnesite.

31. the composition of claim 29, wherein said composition comprises the combination of aragonite and nesquehonite.

32. the composition of claim 29, wherein said composition comprises the combination of nesquehonite and single hydroconite.