U.S. patent application number 16/992318 was filed with the patent office on 2021-03-11 for process to make calcium oxide or ordinary portland cement from calcium bearing rocks and minerals.
The applicant listed for this patent is Brimstone Energy Inc., California Institute of Technology. Invention is credited to Cody E. FINKE, Hugo F. LEANDRI.
Application Number | 20210070656 16/992318 |
Document ID | / |
Family ID | 1000005278319 |
Filed Date | 2021-03-11 |
United States Patent
Application |
20210070656 |
Kind Code |
A1 |
FINKE; Cody E. ; et
al. |
March 11, 2021 |
PROCESS TO MAKE CALCIUM OXIDE OR ORDINARY PORTLAND CEMENT FROM
CALCIUM BEARING ROCKS AND MINERALS
Abstract
Aspects of the invention include a method of producing a cement
material comprising step of: first reacting a calcium-bearing
starting material with a first acid to produce an aqueous first
calcium salt; second reacting the aqueous first calcium salt with a
second acid to produce a solid second calcium salt; wherein the
second acid is different from the first acid and the second calcium
salt is different from the first calcium salt; and thermally
treating the second calcium salt to produce a first cement
material. Preferably, but not necessarily, during the second
reacting step, reaction between the first calcium salt and the
second acid regenerates the first acid.
Inventors: |
FINKE; Cody E.; (Pasadena,
CA) ; LEANDRI; Hugo F.; (Pasadena, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
California Institute of Technology
Brimstone Energy Inc. |
Pasadena
Oakland |
CA
CA |
US
US |
|
|
Family ID: |
1000005278319 |
Appl. No.: |
16/992318 |
Filed: |
August 13, 2020 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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62886137 |
Aug 13, 2019 |
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62913620 |
Oct 10, 2019 |
|
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62932200 |
Nov 7, 2019 |
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63019916 |
May 4, 2020 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C04B 22/064 20130101;
C04B 11/005 20130101; C01G 49/14 20130101; C04B 11/30 20130101;
C07C 1/328 20130101; C04B 28/04 20130101; C01F 7/56 20130101; C04B
40/0046 20130101 |
International
Class: |
C04B 11/00 20060101
C04B011/00; C04B 22/06 20060101 C04B022/06; C04B 40/00 20060101
C04B040/00; C04B 28/04 20060101 C04B028/04; C04B 11/30 20060101
C04B011/30 |
Claims
1. A method of producing a cement material, the method comprising
steps of: first reacting a calcium-bearing starting material with a
first acid to produce an aqueous first calcium salt; second
reacting the aqueous first calcium salt with a second acid to
produce a solid second calcium salt; wherein the second acid is
different from the first acid and the second calcium salt is
different from the first calcium salt; and thermally treating one
or more calcium salts to produce a first cement material.
2. The method of claim 1, wherein the one or more calcium salts
comprises the second calcium salt.
3. The method of claim 1, wherein, during the second reacting step,
reaction between the first calcium salt and the second acid
regenerates the first acid.
4-5. (canceled)
6. The method of claim 1 comprising a first separating step after
the first reacting step and before the second reacting step; the
first separating step comprising separating a first aqueous
fraction from a first solid fraction; wherein the first aqueous
fraction comprises the aqueous first calcium salt and the first
solid fraction comprises one or more solid byproducts formed during
the first reacting step.
7-8. (canceled)
9. The method of claim 1 comprising a second acid regeneration
step; wherein the second acid regeneration step comprises
converting one or more gas products of the thermally treating step
to the second acid.
10-14. (canceled)
15. The method of claim 1, wherein, during the second reacting
step, reaction between the first calcium salt and the second acid
regenerates the first acid according to formula FX3:
CaCl.sub.2(aq)+H.sub.2SO.sub.4->CaSO.sub.4(s)+2HCl (FX3);
wherein: the first calcium salt is CaCl.sub.2); the first acid is
HCl; the second acid is H.sub.2SO.sub.4; and the second calcium
salt is CaSO.sub.4.
16. The method of claim 1, wherein the calcium-bearing starting
material has at least 1 dry wt. % of Ca.
17-18. (canceled)
19. The method of claim 1, wherein the calcium-bearing starting
material comprises at least one natural rock or mineral; wherein
the at least one natural rock or mineral comprises basalt, igneous
appetites, wollastonite, anorthosite, montmorillonite, bentonite,
calcium-containing feldspar, anorthite, diopside, pyroxene,
pyroxenite, mafurite, kamafurite, clinopyroxene, colemonite,
grossular, augite, pigeonite, margarite, calcium serpentine,
garnet, scheilite, skarn, limestone, natural gypsum, appetite,
fluorapatite, or any combination of these.
20-21. (canceled)
22. The method of claim 1, wherein calcium-bearing starting
material comprises cement, concrete, Portland cement, fly ash,
slag, or any combination of these.
23. The method of claim 1, wherein the first acid is hydrochloric
acid and the aqueous first calcium salt is calcium chloride.
24. The method of claim 1, wherein the second acid is sulfuric acid
and/or sulfurous acid.
25. The method of claim 1, wherein the aqueous first calcium salt
is calcium chloride and the solid second calcium salt is calcium
sulfate and/or calcium sulfite.
26-28. (canceled)
29. The method of claim 1, wherein the first reacting step
comprises reacting the calcium-bearing starting material with
hydrochloric acid to form at least aqueous calcium chloride,
aqueous aluminum chloride, and solid silica.
30-32. (canceled)
33. The method of claim 1 comprising a step of forming a composite
cement material; wherein: (i) the thermally treating step comprises
the step of forming the composite cement material and the first
cement material is the composite cement material or (ii) the step
of forming the composite material is performed using the first
cement material formed during the thermally treating step.
34-36. (canceled)
37. The method of claim 33, wherein the composite cement material
is ordinary Portland cement or a Portland cement clinker, and/or
the first cement material is calcium oxide.
38-41. (canceled)
42. The method of claim 1 comprising forming and isolating
silica-fume grade silica, nano-silica, and/or micro-silica from the
calcium-bearing starting material.
43. The method of claim 1 comprising forming and isolating alumina
from the calcium-bearing starting material.
44-47. (canceled)
48. The method of claim 1 comprising forming and isolating iron
oxide from the calcium-bearing starting material.
49. The method of claim 48, wherein the step of forming and
isolating the iron oxide comprises: forming an aqueous solution
having aqueous iron sulfate and/or iron chloride and magnesium
sulfate salt and/or chloride salt formed as byproducts during the
second reacting step; wherein the aqueous solution is free of a
calcium salt; and using SO.sub.2 to precipitate MgSO.sub.3.
50-69. (canceled)
70. A method for producing a cement material via reductive thermal
decomposition, the method comprising steps of: reacting a
calcium-bearing material with a chemically reducing gas to produce
methane and a cement material.
71-82. (canceled)
83. A method of producing a cement material, the method comprising
steps of: first reacting a calcium-bearing starting material with a
first acid to produce a first aqueous fraction comprising an
aqueous first calcium salt and a first solid fraction comprising
one or more solid byproducts; wherein: the calcium-bearing starting
material has a chemical composition comprising a plurality of metal
elements including at least Ca and Si; the one or more solid
byproducts comprises a silicon salt; first separating the first
aqueous fraction from the first solid fraction; and treating the
first calcium salt to produce a first cement material.
84-95. (canceled)
96. The method of claim 1, wherein the first reacting step
comprises reacting the calcium-bearing starting material with
hydrochloric acid to form at least aqueous calcium chloride,
aqueous aluminum chloride, aqueous iron chloride, aqueous magnesium
chloride, and solid silica.
97. (canceled)
98. The method of claim 96, wherein the second reacting step
comprises reacting at least the aqueous calcium chloride, and
sulfuric acid to form at least solid calcium sulfate, solid calcium
sulfate, and hydrochloric acid.
99. (canceled)
100. The method of claim 1, comprising forming and isolating
aluminum chloride and forming aluminum metal via electrowinning the
aluminum chloride.
101. (canceled)
102. The method of claim 1, comprising forming and isolating iron
sulfate and forming iron metal via electrowinning the iron
sulfate.
103. (canceled)
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of and priority to U.S.
Provisional Application No. 62/886,137, filed Aug. 13, 2019, U.S.
Provisional Application No. 62/913,620, filed Oct. 10, 2019, U.S.
Provisional Application No. 62/932,200, filed Nov. 7, 2019, and
U.S. Provisional Application No. 63/019,916, filed May 4, 2020,
each of which is hereby incorporated by reference in its entirety
to the extent not inconsistent herewith.
BACKGROUND OF INVENTION
[0002] The art of producing cement materials, including Ordinary
Portland Cement, faces considerable challenges, inefficiencies,
and/or drawbacks. For example, conventional processes for producing
cement are energy intensive, produce environment-degrading
byproducts such as CO.sub.2 and/or SO.sub.2, and utilize only a
limited range of feedstocks, primarily simple calcium-based
materials such as calcium carbonate (limestone) or mined calcium
sulfate (gypsum). This application addresses these and other
challenges in the art.
SUMMARY OF THE INVENTION
[0003] Provided herein are methods for producing cement materials
that have any combination of the following advantages or features:
less energy intensive than prior approaches, with some embodiments
being net energy neutral or even net energy producing, regenerate
certain reagents, characterized by a net reaction free of SO.sub.2
and/or CO.sub.2, recycle certain byproducts, do not include
producing CO.sub.2, can utilize a wider range of feedstock
materials, including more complex materials, generate value-added
side products, and/or generate composite cement materials.
[0004] Included herein are methods for producing cement materials
using a two-acid approach, where materials are reacted with two
different acids and/or two different acid reaction steps.
Advantages of these approaches include all or a majority of the
above mentioned advantages and features. For example, the disclosed
two-acid approach provides for the ability to digest complex
calcium-bearing materials, including those with Ca as well as other
metal (including metalloid) elements such Si, Al, and other
species, and even forming value-added side products from those
non-Ca metals, while also regenerating reagent acids.
Significantly, these methods can also be free of CO.sub.2
generation and can include converting SO.sub.2 into a reagent acid,
thereby eliminating or dramatically reducing SO.sub.2 emissions for
CaSO.sub.4 based approaches to cement manufacturing.
[0005] Aspects of the invention include a method of producing a
cement material comprising steps of: first reacting a
calcium-bearing starting material with a first acid to produce an
aqueous first calcium salt; second reacting the aqueous first
calcium salt with a second acid to produce a solid second calcium
salt; wherein the second acid is different from the first acid and
the second calcium salt is different from the first calcium salt;
and thermally treating one or more calcium salts to produce a first
cement material. Preferably, but not necessarily, the one or more
calcium salts is the second calcium salt. Preferably, but not
necessarily, during the second reacting step, reaction between the
first calcium salt and the second acid regenerates the first acid.
Preferably, but not necessarily, the methods are characterized by a
net reaction free of an acid-forming gas product. Preferably, but
not necessarily, the method comprises forming the solid second
calcium salt characterized by a purity of greater than or equal to
90 dry wt. % purity. Preferably, but not necessarily, any of the
methods disclosed herein include a first separating step after the
first reacting step and before the second reacting step; the first
separating step comprising separating a first aqueous fraction from
a first solid fraction; wherein the first aqueous fraction
comprises the aqueous first calcium salt and the first solid
fraction comprises one or more solid byproducts formed during the
first reacting step. Preferably, but not necessarily, any of the
methods disclosed herein include a second separating step after the
second reacting step and before the thermally treating step; the
second separating step comprising separating a second solid
fraction from a second aqueous fraction; wherein the second solid
fraction comprises the solid second calcium salt and the second
aqueous fraction comprises one or more aqueous byproducts formed
during the second reacting step. Preferably, the solid fraction is
characterized by a dry mass at least 90 wt. % of which is the
second calcium salt.
[0006] Preferably, but not necessarily, any of the methods
disclosed herein include a second acid regeneration step; wherein
the second acid regeneration step comprises converting one or more
gas products of the thermally treating step to the second acid.
Optionally, the second acid regeneration step is a
non-electrochemical process performed according to formula FX1A:
SO.sub.2+1/2O.sub.2+H.sub.2O.fwdarw.H.sub.2SO.sub.4 (FX1A) wherein:
the SO.sub.2 in FX1A is a gas product of the thermally treating
step; the H.sub.2SO.sub.4 generated in FX1A is used as at least a
fraction of the second acid during the second reacting step.
Optionally, the second acid regeneration step is a
non-electrochemical process performed according to formula FX1B:
SO.sub.2+H.sub.2O.fwdarw.H.sub.2SO.sub.3 (FX1B) wherein: the
SO.sub.2 in FX1B is a gas product of the thermally treating step;
the H.sub.2SO.sub.3 generated in FX1B is used as at least a
fraction of the second acid during the second reacting step.
Optionally, the second acid regeneration step comprises (i)
electrochemically oxidizing sulfur dioxide to sulfuric acid and
(ii) forming hydrogen gas via a reduction reaction; and wherein the
second acid regeneration step is performed according to formula
FX2: SO.sub.2+2H.sub.2O H.sub.2SO.sub.4+H.sub.2 (FX2); wherein: the
SO.sub.2 in FX2 is a gas product of the thermally treating step;
the H.sub.2SO.sub.4 generated in FX2 is used as at least a fraction
of the second acid during the second reacting step. Optionally, the
thermally treating step comprises using energy generated from
oxidizing the hydrogen gas formed as a result of the second acid
regeneration. For example, the hydrogen gas produced via the method
can be used to power the electrochemical step, such as via a fuel
cell or turbine. Optionally, the electrochemically oxidizing sulfur
dioxide comprises using energy generated as a result of the second
acid regeneration step. It is noted that when H.sub.2SO.sub.4 is
added to a solution that contains both MgCl.sub.2 and CaCl.sub.2),
only CaSO.sub.4 will precipitate. If H.sub.2SO.sub.3 is added to a
solution of MgCl.sub.2 and CaCl.sub.2), both MgSO.sub.3 and
CaSO.sub.3 will precipitate. Of consideration is that there are
currently regulations against having Mg in cement, such that the
calcium-bearing starting material preferably has a low-Mg content
so minimize amount of Mg material precipitated.
[0007] Optionally, during the second reacting step, reaction
between the first calcium salt and the second acid regenerates the
first acid according to formula FX3:
CaCl.sub.2(aq)+H.sub.2SO.sub.4->CaSO.sub.4 (s) 2HCl (FX3);
wherein: the first calcium salt is CaCl.sub.2); the first acid is
HCl; the second acid is H.sub.2SO.sub.4; and the second calcium
salt is CaSO.sub.4.
[0008] The calcium-bearing starting material comprises Ca. The
calcium-bearing starting material has a chemical composition
comprising the element Ca. Preferably, the calcium-bearing starting
material has a chemical composition comprising the element Ca
wherein the weight percent and/or the molar percent of Ca in said
calcium-bearing starting material is at least 0.001%, preferably at
least 0.01%, preferably at least 0.1%, more preferably at least 1%,
further more preferably at least 5%, still more preferably at least
10%, and yet more preferably at least 20%. Optionally, in any of
the methods disclosed herein, the calcium-bearing starting material
has a chemical composition comprising the element Ca wherein the
weight percent and/or the molar percent of Ca in said
calcium-bearing starting material is selected from the range of 1%
to 80%, optionally 1% to 60%, optionally 1% to 55%, optionally 1%
to 50%. Optionally, in any of the methods disclosed herein, the
calcium-bearing starting material comprises at least one multinary
metal oxide material having a composition comprising Ca and at
least one other metal element selected from the group consisting of
Al, Si, Fe, Mn, and Mg. Optionally, the composition of the at least
one multinary metal oxide comprises less than or equal to 55 wt. %
of Ca. Optionally, the composition of the at least one multinary
metal oxide comprises less than or equal to 60 wt. % of Ca.
Optionally, in any of the methods disclosed herein, the at least
one multinary metal oxide material is at least one natural rock or
mineral. Optionally, in any of the methods disclosed herein, the at
least one natural rock or mineral comprises basalt, igneous
appetites, wollastonite, anorthosite, montmorillonite, bentonite,
calcium-containing feldspar, anorthite, diopside, pyroxene,
pyroxenite, mafurite, kamafurite, clinopyroxene, colemonite,
grossular, augite, pigeonite, margarite, calcium serpentine,
garnet, scheilite, skarn, limestone, natural gypsum, appetite,
fluorapatite, or any combination of these. Optionally, in any of
the methods disclosed herein, calcium-bearing starting material
comprises cement, concrete, Portland cement, fly ash, slag, or any
combination of these. If the calcium-bearing starting material
comprises CaCO.sub.3, then CO.sub.2 may be generated during the
method. However, wherein CO.sub.2 is generated, the CO.sub.2 is at
a high concentration and can be stored and/or utilized.
[0009] Optionally, in any of the methods disclosed herein, the
first acid comprises hydrochloric acid (HCl). Optionally, in any of
the methods disclosed herein, the first acid is hydrochloric acid.
Optionally, in any of the methods disclosed herein, the second acid
comprises sulfuric acid (H.sub.2SO.sub.4) and/or sulfurous acid
(H.sub.2SO.sub.3). Optionally, in any of the methods disclosed
herein, the second acid is sulfuric acid and/or sulfurous acid.
Optionally, in any of the methods disclosed herein, the second acid
is sulfuric acid. Optionally, in any of the methods disclosed
herein, the second acid is sulfurous acid. Optionally, in any of
the methods disclosed herein, the aqueous first calcium salt is
calcium chloride (CaCl.sub.2)). Optionally, in any of the methods
disclosed herein, the solid second calcium salt is calcium sulfate
(CaSO.sub.4) and/or calcium sulfite (CaSO.sub.3). Optionally, in
any of the methods disclosed herein, the solid second calcium salt
is calcium sulfate. Optionally, in any of the methods disclosed
herein, the solid second calcium salt is calcium sulfite
(CaSO.sub.3). Preferably, in any of the methods disclosed herein,
the first cement material comprises CaO. Optionally, in any of the
methods disclosed herein, the first cement material is calcium
oxide (CaO). Optionally, in any of the methods disclosed herein,
the first cement material is calcium oxide (CaO) or Portland cement
clinker. Optionally, in any of the methods disclosed herein, the
first cement material is Portland cement clinker. Optionally, in
any of the methods disclosed herein, the acid-forming gas product
is SO.sub.2 and/or CO.sub.2. Optionally, in any of the methods
disclosed herein, the acid-forming gas product is SO.sub.2.
Optionally, in any of the methods disclosed herein, the
acid-forming gas product is CO.sub.2.
[0010] Preferably, but not necessarily, in any of the methods
disclosed herein, the first reacting step comprises reacting the
calcium-bearing starting material with hydrochloric acid to form at
least aqueous calcium chloride, aqueous aluminum chloride, and
solid silica. Preferably, but not necessarily, in any of the
methods disclosed herein, the first separating step comprises
separating a first aqueous fraction comprising the aqueous calcium
chloride and the aqueous aluminum chloride from a first solid
fraction comprising the solid silica. Preferably, but not
necessarily, in any of the methods disclosed herein, the second
reacting step comprises reacting at least the aqueous calcium
chloride, the aqueous aluminum chloride, and sulfuric acid to form
at least solid calcium sulfate, aqueous aluminum sulfate, and
hydrochloric acid. Preferably, but not necessarily, in any of the
methods disclosed herein, the thermally treating step comprises
heating the calcium sulfate to form calcium oxide.
[0011] Preferably, but not necessarily, in any of the methods
disclosed herein, the first reacting step comprises reacting the
calcium-bearing starting material with hydrochloric acid to form at
least aqueous calcium chloride, aqueous aluminum chloride, aqueous
iron chloride, aqueous magnesium chloride, and solid silica.
Preferably, but not necessarily, in any of the methods disclosed
herein, the first separating step comprises separating a first
aqueous fraction comprising the aqueous calcium chloride and the
aqueous aluminum chloride from a first solid fraction comprising
the solid silica. Preferably, but not necessarily, in any of the
methods disclosed herein, the second reacting step comprises
reacting at least the aqueous calcium chloride, and sulfuric acid
to form at least solid calcium sulfate, solid calcium sulfate, and
hydrochloric acid. Preferably, but not necessarily, in any of the
methods disclosed herein, the thermally treating step comprises
heating the calcium sulfate to form calcium oxide.
[0012] Optionally, any of the methods disclosed herein comprises an
ion exchange step; wherein the ion exchange step comprises
exchanging one or more anions of the first calcium salt and/or the
second calcium salt for one or more hydroxyl anions to form a third
calcium salt. Optionally, the ion exchange step comprises reacting
the first calcium salt and/or the second calcium salt with a
chelating agent to form a calcium-chelator compound and reacting
the calcium-chelator compound with a base to form the third calcium
salt. Optionally, the ion exchange step comprises reacting the
first calcium salt and/or the second calcium salt with a base to
form the third calcium salt. Optionally, the ion exchange step
comprises using an ion exchange membrane to perform the exchanging
one or more anions of the first calcium salt and/or the second
calcium salt for one or more hydroxyl anions to form the third
calcium salt. Optionally, the one or more calcium salts of the
thermally treating step is the third calcium salt. Optionally, the
third calcium salt is Ca(OH).sub.2. Optionally, any of the methods
disclosed herein comprises a step of regenerating the chelating
agent, wherein the step of regenerating the chelating agent
comprises producing the third calcium salt. Optionally, any of the
methods disclosed herein comprises a step of forming the first
cement material from the third calcium salt. Optionally, the step
of forming the first cement material from the third calcium salt
comprises dehydrating the third calcium salt or directly releasing
the first cement material from the calcium-chelator compound,
optionally via a base. For example, CaO can be formed by using a
chelating agent or base to react the CaCl.sub.2), CaSO.sub.3, or
CaSO.sub.4. For example, then the chelating agent or base can be
regenerated in a manner that releases Ca(OH).sub.2 which can be
dehydrated to CaO or CaO could be directly released from the
chelator. For example, if CaSO.sub.4 is precipitated, a chelating
agent such as EDTA can be reacted with CaSO.sub.4 to make Ca-EDTA.
For example, a base such as NaOH can then be used to directly
produce Ca(OH).sub.2 and regenerate the EDTA.
[0013] Preferably, but not necessarily, any method disclosed herein
comprises a step of forming a composite cement material; wherein:
(i) the thermally treating step comprises the step of forming the
composite cement material and the first cement material is the
composite cement material or (ii) the step of forming the composite
material is performed using the first cement material formed during
the thermally treating step. For example, wherein the step of
forming the composite material is performed using the first cement
material formed during the thermally treating step, the formation
of the composite material can occur simultaneously with formation
of the first cement material (e.g., CaO) or subsequently after
formation of the first cement material (e.g., CaO). Optionally, any
method disclosed herein comprises a step of forming a composite
cement material; wherein the thermally treating step comprises the
step of forming the composite cement material and the first cement
material is the composite cement material. Optionally, any method
disclosed herein comprises a step of forming a composite cement
material; wherein the step of forming the composite material is
performed using the first cement material formed during the
thermally treating step. Optionally, in any of the methods
disclosed herein, the step of forming the composite cement material
comprises heating the second calcium salt and/or the first cement
material together with one or more additives. Optionally, in any of
the methods disclosed herein, the step of forming the composite
cement material comprises heating the second calcium salt together
with one or more additives. Optionally, in any of the methods
disclosed herein, the step of forming the composite cement material
comprises heating the first cement material together with one or
more additives. Optionally, in any of the methods disclosed herein,
the step of forming the composite cement material is performed
simultaneously with the thermally treating step. Optionally, in any
of the methods disclosed herein, after the thermally treating step.
Optionally, in any of the methods disclosed herein, the composite
cement material is Portland cement clinker. Optionally, in any of
the methods disclosed herein, the composite cement material is
ordinary Portland cement and/or the first cement material is
calcium oxide. Optionally, in any of the methods disclosed herein,
the first cement material is calcium oxide. Optionally, in any of
the methods disclosed herein, the composite cement material is
ordinary Portland cement. Optionally, any method disclosed herein
comprises forming the one or more additives from the
calcium-bearing starting material. Optionally, in any of the
methods disclosed herein, the one or more additives are one or more
byproducts of the first reacting step and/or are formed from one or
more byproducts of the first reacting step and/or are one or more
byproducts of the second reacting step and/or are formed from one
or more byproducts of the second reacting step. Optionally, in any
of the methods disclosed herein, the one or more additives are one
or more byproducts of the first reacting step and/or are formed
from one or more byproducts of the first reacting step. Optionally,
in any of the methods disclosed herein, the one or more additives
are one or more byproducts of the second reacting step and/or are
formed from one or more byproducts of the second reacting step.
Optionally, in any of the methods disclosed herein, the one or more
additives are one or more byproducts of the first reacting step.
Optionally, in any of the methods disclosed herein, the one or more
additives are one or more byproducts of the second reacting step.
Optionally, in any of the methods disclosed herein, the one or more
additives are one or more byproducts of the first reacting step
and/or are one or more byproducts of the second reacting step.
Optionally, in any of the methods disclosed herein, a combined
chemical composition of the one or more additives comprises Al and
Si. Optionally, in any of the methods disclosed herein, the one or
more additives are at least Al.sub.2O.sub.3 and SiO.sub.2.
[0014] An advantage of the methods disclosed herein is that
value-added side products can be formed. For example, instead of
using simple calcium sources such as limestone or gypsum as
starting materials, one can use complex minerals that include Ca
and Si, and optionally other metals such as Al, Mg, and/or Fe.
Instead of being undesired elements that contaminate the cement
product, for example, the methods disclosed herein can include
steps to form and isolate valuable products having these extra
elements, such as oxides of Al, oxides of Mg, and/or oxides of Fe.
These steps do not contribution significant additional operational
costs.
[0015] Preferably, but not necessarily, any method disclosed herein
comprises forming and isolating silica-fume grade silica,
nano-silica, and/or micro-silica from the calcium-bearing starting
material. Preferably, but not necessarily, any method disclosed
herein comprises forming and isolating alumina from the
calcium-bearing starting material.
[0016] Preferably, but not necessarily, in any method disclosed
herein, the first reacting step comprises reacting the
calcium-bearing starting material with hydrochloric acid to form at
least aqueous aluminum chloride; wherein the method further
comprises: precipitating the aluminum chloride in the presence of
hydrochloric acid; and optionally reacting the precipitated
aluminum chloride with sulfuric acid to form solid aluminum
sulfate; heating the aluminum sulfate and/or aluminum chloride to
form alumina. Preferably, but not necessarily, in any method
disclosed herein, the hydrochloric acid is regenerated in these
steps. Preferably, but not necessarily, in any method disclosed
herein, the reaction of the precipitated aluminum chloride forms
hydrochloric acid. Preferably, but not necessarily, in any method
disclosed herein, the hydrochloric acid is regenerated in these
steps. Preferably, but not necessarily, in any method disclosed
herein, the second reacting step comprises the step of reacting the
precipitated aluminum chloride. Optionally, in any of the methods
disclosed herein, the thermally treating step comprises the heating
the aluminum sulfate step. Optionally, in any of the methods
disclosed herein, the thermally treating step comprises the heating
the aluminum chloride step.
[0017] Optionally, any method disclosed herein comprises forming
and isolating iron oxide from the calcium-bearing starting
material. Optionally, in any of the methods disclosed herein, the
forming and isolating the iron oxide comprises: forming an aqueous
solution having aqueous iron sulfate and/or iron chloride and
optionally at least one other metal magnesium sulfate salt and/or
chloride salt formed as byproducts during the second reacting step;
wherein the aqueous solution is free of a calcium salt and free of
an aluminum salt; drying the aqueous solution to form solid iron
sulfate and/or solid iron chloride and optionally the at least one
other metal sulfate salt; heating the solid iron sulfate and
optionally the at least one other metal sulfate salt to form a
water-insoluble iron oxide; and optionally, dissolving the at least
one other metal sulfate salt to isolate the water-insoluble iron
oxide.
[0018] Optionally, any method disclosed herein comprises forming
and isolating iron oxide from the calcium-bearing starting
material. Optionally, in any of the methods disclosed herein, the
forming and isolating the iron oxide comprises: forming an aqueous
solution having aqueous iron sulfate or iron chloride and
optionally at least one other metal magnesium sulfate or chloride
salt formed as byproducts during the second reacting step; wherein
the aqueous solution is free of a calcium salt and free of an
aluminum salt; using SO.sub.2 to precipitate MgSO.sub.3; separating
the aqueous iron salt from the solid magnesium salt; drying the
aqueous solution to form solid iron sulfate or chloride and
optionally the at least one other metal sulfate salt; heating the
solid iron sulfate and optionally the at least one other metal
sulfate salt to form a water-insoluble iron oxide; and optionally,
dissolving the at least one other metal sulfate salt to isolate the
water-insoluble iron oxide.
[0019] Optionally, iron chloride, iron sulfate, aluminum chloride,
and/or aluminum sulfate, and/or any other iron and/or aluminum salt
is produced and sold and/or combined with electrochemical
strategies to make iron and aluminum metals from the aluminum
chloride, sulfate, and/or other salts. For example, aluminum
chloride can be isolated and aluminum can be electrowon from
aluminum chloride while co-producing chlorine gas. This chlorine
gas can then be reacted with hydrogen, possibly hydrogen from the
cogeneration of sulfuric acid and hydrogen to regenerate HCl.
Another example is iron can be electrowon from iron sulfate to
regenerate sulfuric acid.
[0020] Methods disclosed herein can comprise one or more
acid-forming reactions. An acid-forming reaction can be a reaction
to regenerate an acid that is consumed in a different reaction of
the method. The acid-forming reaction can be a reaction that
supplies the acid to the (first and/or second) reacting step
wherein the acid is consumed. For example, instead of supplying an
acid to a reacting step, where the acid is consumed to form a
calcium salt, reagents that form said acid are supplied to the
reacting step such that said reacting step comprises both forming
the acid and the respective acid consumption (or, salt forming)
reaction.
[0021] Preferably, but not necessarily, any method disclosed herein
comprises a step of forming the first acid; wherein: (i) the first
reacting step comprises the step of forming the first acid and the
step of forming the first acid occurs simultaneously with the first
reacting step, or (ii) the step of forming the first acid is
performed separately from the first reacting step. Optionally, any
method disclosed herein comprises a step of forming the first acid;
wherein the first reacting step comprises the step of forming the
first acid and the step of forming the first acid is occurs
simultaneously with the first reacting step. Optionally, any method
disclosed herein comprises a step of forming the first acid;
wherein the step of forming the first acid is performed separately
from the first reacting step.
[0022] Preferably, but not necessarily, any method disclosed herein
comprises a step of forming the second acid; wherein: (i) the
second reacting step comprises the step of forming the second acid
and the step of forming the second acid occurs simultaneously with
the second reacting step, or (ii) the step of forming the second
acid is performed separately from the second reacting step.
Optionally, any method disclosed herein comprises a step of forming
the second acid; wherein the second reacting step comprises the
step of forming the second acid and the step of forming the second
acid occurs simultaneously with the second reacting step.
Optionally, any method disclosed herein comprises a step of forming
the second acid; wherein the step of forming the second acid is
performed separately from the second reacting step. Optionally, in
any of the methods disclosed herein, the step of forming the second
acid comprises reacting SO.sub.2 with water to form H.sub.2SO.sub.3
and/or H.sub.2SO.sub.4; wherein the second acid is H.sub.2SO.sub.3
and/or H.sub.2SO.sub.4. Optionally, in any of the methods disclosed
herein, the second acid is H.sub.2SO.sub.3 and/or H.sub.2SO.sub.4
and wherein the second calcium salt is CaSO.sub.3 and/or
CaSO.sub.4, respectively.
[0023] Optionally, in any of the methods disclosed herein, the
first acid and/or the second acid is a bulk acid. Optionally, in
any of the methods disclosed herein, the first acid is a bulk acid.
Optionally, in any of the methods disclosed herein, the second acid
is a bulk acid.
[0024] Optionally, in any of the methods disclosed herein, the step
of forming the first acid comprises forming a pH gradient via water
electrolysis; wherein the first acid is formed via the water
electrolysis. Optionally, in any of the methods disclosed herein,
the step of forming the second acid comprises forming a pH gradient
via water electrolysis; wherein the second acid is formed via the
water electrolysis.
[0025] Optionally, in any of the methods disclosed herein, the
second acid regeneration step according to formula FX1A is
performed at a temperature selected from the range of 400.degree.
C. to 1800.degree. C. Optionally, in any of the methods disclosed
herein, the second acid regeneration step according to formula FX1A
is performed at a temperature selected from the range of
400.degree. C. to 600.degree. C. Optionally, in any of the methods
disclosed herein, the second acid regeneration step according to
formula FX1A is performed at a temperature selected from the range
of 400.degree. C. to 600.degree. C., is exothermic, and is
performed in the presence of a catalyst. Optionally, the catalyst
comprises vanadium oxide. Optionally, in any of the methods
disclosed herein, the method is characterized by a net energy
selected from the range of -2 to +2 GJ per metric ton of produced
cement material (e.g., produced first cement material or produced
composite cement material, such as OPC). Optionally, in any of the
methods disclosed herein, the method is characterized by a net
energy selected from the range of -10 to +10 GJ/t, optionally -5 to
+5 GJ/t, optionally -5 to +4 GJ/t, optionally -5 to +3 GJ/t,
optionally -5 to +2 GJ/t, optionally -5 to +1 GJ/t, optionally -5
to +0.5 GJ/t, optionally -5 to +0.2 GJ/t, optionally -5 to +0.1
GJ/t, optionally -5 to 0 GJ/t, optionally -2 to 1 GJ/t, optionally
-2 to -1.5 GJ/t, optionally -2 to +1.0 GJ/t, optionally -2 to +0.5
GJ/t, optionally -2 to +0.3 GJ/t, optionally -2 to +0.2 GJ/t,
optionally -2 to +0.1 GJ/t, optionally -2 to +0 GJ/t. Optionally,
in any of the methods disclosed herein, the first reacting step is
exothermic. Optionally, in any of the methods disclosed herein, the
second acid regeneration step is exothermic. Optionally, in any of
the methods disclosed herein, the first reacting step is performed
at a temperature of at least 50.degree. C. Optionally, in any of
the methods disclosed herein, the first reacting step is performed
at a temperature selected from the range of 80.degree. C. to
100.degree. C., preferably 90.+-.5.degree. C. Optionally, in any of
the methods disclosed herein, the thermally treating step is
performed at a temperature selected from the range of 1100.degree.
C. to 1800.degree. C. Optionally, in any of the methods disclosed
herein, the thermally treating step comprises thermally treating
the second calcium salt in the presence of a chemical reductant and
is performed at a temperature selected from the range of
800.degree. C. to 1200.degree. C. Optionally, the chemical
reductant is water, carbon (or any allotrope or combination of
allotropes of carbon, hydrogen gas, methane, gas, or any
combination of these. Optionally, the chemical reductant is water,
carbon (or any allotrope or combination of allotropes of carbon,
methane, gas, or any combination of these. Optionally, the
thermally treating step can be performed according to any one or a
combination of formulas FX4A, FX4B, FX4C, and FX4D:
CaSO.sub.4+H.sub.2O.fwdarw.CaO+H.sub.2SO.sub.4 (FX4A);
CaSO.sub.4+2C CaS+2CO.sub.2 (FX4B);
CaSO.sub.4+CH.sub.4.fwdarw.CaS+CO.sub.2+2H.sub.2O (FX4C);
CaS+3CaSO.sub.4.fwdarw.4CaO (FX4D).
[0026] Any of the methods disclosed herein can be performed as a
batch process, a plug flow process, a semi-continuous process, a
staged process, a continuous process, or any combination of these.
Any of step of any method disclosed herein can be performed as a
batch process, a plug flow process, a semi-continuous process, a
staged process, a continuous process, or any combination of
these.
[0027] Additional aspects of the invention disclosed herein include
a method for producing a cement material via reductive thermal
decomposition, the method comprising steps of: reacting a
calcium-bearing material with a chemically reducing gas to produce
methane and a cement material. Preferably, but not necessarily, in
any method for producing a cement material via reductive thermal
decomposition, the calcium-bearing material comprises CaCO.sub.3,
CaSO.sub.4, CaS, a calcium salt, or any combination thereof.
Preferably, but not necessarily, in any method for producing a
cement material via reductive thermal decomposition, the
calcium-bearing material is CaCO.sub.3, CaSO.sub.4, CaS, or any
combination thereof. Preferably, but not necessarily, in any method
for producing a cement material via reductive thermal
decomposition, the calcium-bearing material is CaCO.sub.3.
Preferably, but not necessarily, in any method for producing a
cement material via reductive thermal decomposition, the
calcium-bearing material comprises CaCO.sub.3. Preferably, but not
necessarily, in any method for producing a cement material via
reductive thermal decomposition, the chemically reducing gas is
hydrogen gas or a gas that comprises hydrogen gas, such as forming
gas. Preferably, but not necessarily, in any method for producing a
cement material via reductive thermal decomposition, the cement
material comprises CaO. Preferably, but not necessarily, in any
method for producing a cement material via reductive thermal
decomposition, the cement material is CaO. Preferably, but not
necessarily, in any method for producing a cement material via
reductive thermal decomposition, a molar ratio of calcium-bearing
material reacting with the chemically reducing gas is 1:4 or 1:2.
Optionally, in any method for producing a cement material via
reductive thermal decomposition, the reacting is performed in the
presence of water. Optionally, in any method for producing a cement
material via reductive thermal decomposition, the reacting is
performed in the absence of water. Optionally, in any method for
producing a cement material via reductive thermal decomposition,
the molar ratio of CaCO.sub.3 reacts with hydrogen gas at a molar
ratio of 1:4 during the step of reacting. Optionally, in any method
for producing a cement material via reductive thermal
decomposition, the molar ratio of CaCO.sub.3 reacts with hydrogen
gas at a molar ratio of 1:2 during the step of reacting. Generally,
the reaction according to a 1:4 molar ratio is lower energy but
high OpEx because more H.sub.2 needs to be made, but a lower temp
can be used. Generally, the reaction according to a 1:2 molar ratio
has a higher energy but lower OpEx. Optionally, in any method for
producing a cement material via reductive thermal decomposition,
oxygen gas, water, or a combination of oxygen gas and water is
produced during the step of reacting. Optionally, any method for
producing a cement material via reductive thermal decomposition
comprises a step of decomposing the methane to produce hydrogen gas
and one or more carbon materials. Optionally, in any method for
producing a cement material via reductive thermal decomposition,
the method does not comprise forming CO.sub.2. Optionally, in any
method for producing a cement material via reductive thermal
decomposition, the step of reacting is characterized by a lower
heating value (LHV) of 720 kJ/mol or less and a high heating value
(HHV) of 800 kJ/mol or less. Optionally, in any method for
producing a cement material via reductive thermal decomposition,
the step of reacting is performed at a temperature of at least
700.degree. C.
[0028] Additional aspects of the invention disclosed herein include
methods for producing a cement material according to a single-acid
approach, wherein only one acid or only one acid reaction step is
needed. In an aspect, a method of producing a cement material
comprises steps of: first reacting a calcium-bearing starting
material with a first acid to produce a first aqueous fraction
comprising an aqueous first calcium salt and a first solid fraction
comprising one or more solid byproducts; wherein: the
calcium-bearing starting material has a chemical composition
comprising a plurality of metal elements including at least Ca and
Si; the one or more solid byproducts comprises a silicon salt;
first separating the first aqueous fraction from the first solid
fraction; and treating the first calcium salt to produce a first
cement material. Optionally, the treating step comprises thermally
treating (or, thermally decomposing) the first calcium salt in the
presence of water to produce the first cement material. Optionally,
thermally treating (or, thermally decomposing) the first calcium
salt regenerates the first acid. Optionally, the treating step
comprises an ion exchange step; wherein the ion exchange step
comprises exchanging the one or more anions of the first calcium
salt for one or more hydroxyl anions to form a third calcium salt.
Optionally, the ion exchange step comprises reacting the first
calcium salt with a chelating agent to form a calcium-chelator
compound and reacting the calcium-chelator compound with a base to
form the third calcium salt. Optionally, the ion exchange step
comprises reacting the first calcium salt with a base to form the
third calcium salt. Optionally, the ion exchange step comprises
using an ion exchange membrane to perform the exchanging one or
more anions of the first calcium salt for hydroxyl anions to form
the third calcium salt. Preferably, the third calcium salt is
Ca(OH).sub.2. Optionally, the treating step comprises thermally
treating (or, thermally decomposing) the third calcium salt to
produce the first cement material. Optionally, the base is a
hydroxide compound. Optionally, the first calcium salt is
CaCl.sub.2). Optionally, for example, the treating step comprises
thermally decomposing CaCl.sub.2) in presence of air according to
formula: CaCl.sub.2)+02->CaO+Cl.sub.2+1/2O.sub.2. Optionally,
for example, the treating step comprises thermally treating
CaCl.sub.2 in the presence of water according to formula:
CaCl.sub.2+H.sub.2O->CaO+2HCl. Optionally, for example, the
treating step comprises ion exchange using an ion exchange membrane
to exchange Cl ions for OH ions thereby forming Ca(OH).sub.2.
Optionally, the treating step further comprises dehydrating the
Ca(OH).sub.2 to make the first cement material. Optionally, for
example, the treating step comprises reacting the first calcium
salt with a chelating agent to form a calcium-chelator compound.
Optionally, for example, the treating step comprises reacting a
base such as NaOH, Mg(OH).sub.2, or MgCl(OH), with the first
calcium salt, such as CaCl.sub.2 to form Ca(OH).sub.2. Optionally,
for example, the treating step further comprises thermally
decomposing Ca(OH).sub.2 to make the first cement material. The
first cement material optionally is or optionally comprises CaO.
Optionally, the first acid is hydrogen chloride. Optionally, the
one or more solid byproducts comprise SiO.sub.2. Optionally, the at
least one multinary metal oxide material is at least one natural
rock or mineral.
[0029] Optionally, in any of the methods disclosed herein, the
first calcium salt and/or the second calcium salt is other than
Ca(OH).sub.2 or comprises a salt other than Ca(OH).sub.2.
Optionally, in any of the methods disclosed herein, the first
reacting step is not an electrochemical step. Optionally, in any of
the methods disclosed herein, the second reacting step is not an
electrochemical step. Optionally, in any of the methods disclosed
herein, the calcium-bearing starting material is other than
CaCO.sub.3 or comprises a material other than CaCO.sub.3.
[0030] Without wishing to be bound by any particular theory, there
may be discussion herein of beliefs or understandings of underlying
principles relating to the devices and methods disclosed herein. It
is recognized that regardless of the ultimate correctness of any
mechanistic explanation or hypothesis, an embodiment of the
invention can nonetheless be operative and useful.
BRIEF DESCRIPTION OF THE DRAWINGS
[0031] FIG. 1. A plot showing methane production in a tube furnace
in partial pressure of methane versus temperature. 0.3 lpm of
forming gas (5% H.sub.2, 95% N.sub.2) flow rate.
[0032] FIG. 2. A plot showing methane production in a tube furnace
in mole methane versus time. 0.3 lpm of forming gas (5% H.sub.2,
95% N.sub.2) flow rate.
[0033] FIG. 3. An XPS pattern of a product obtained from reacting
CaCO.sub.3 in a reducing environment illustrating the pure CaO
appears to be produced.
STATEMENTS REGARDING CHEMICAL COMPOUNDS AND NOMENCLATURE
[0034] In general, the terms and phrases used herein have their
art-recognized meaning, which can be found by reference to standard
texts, journal references and contexts known to those skilled in
the art. The following definitions are provided to clarify their
specific use in the context of the invention.
[0035] The terms "thermal conversion" and "thermally converting"
refer to the conversion of a first chemical species to a second
chemical species via a thermally-activated or thermally-driven
process, which may also be referred to as a thermochemical process.
An exemplary process for thermal conversion of a chemical species
is burning, though thermal conversion processes are not necessarily
limited thereto. For example, thermal conversion of sulfur to
sulfur dioxide may include burning of the sulfur, such as via a
sulfur burner system. Thermal oxidation of a species is a form of
thermal conversion of the species. For example, thermal conversion
of sulfur to sulfur dioxide may be referred to as thermal oxidation
of the sulfur to sulfur dioxide. In some embodiments, thermal
conversion may be aided by a catalyst. In some embodiments, thermal
conversion does not require a catalyst or is performed without a
catalyst. It should be noted that thermal oxidation and
electrochemical oxidation are different processes, where thermal
oxidation is driven or activated thermally (via heat or burning)
and electrochemical oxidation is driven electrochemically (e.g.,
via applying or withdrawing electrical energy, optionally with the
aid of an electrochemical catalyst). The term "thermally treating"
refers thermal treatment or exposure to heat, preferably in excess
of room temperature heat, of one or more materials (such as a
calcium salt, such as CaSO.sub.4) such that the one or more
material may thermally convert, thermally decompose, or otherwise
experience a heat-induced chemical change into another material
(such as a cement material, such as CaO). For example, calcium
sulfate (gypsum) may thermally convert/decompose into calcium oxide
(CaO), along with formation of byproducts such as SO.sub.2 and
oxygen. A thermal treatment may also cause a plurality of
materials, such as a plurality of materials comprising calcium,
aluminum, and silicon, to convert into or otherwise form a
composite cement material, such as Ordinary Portland Cement
(OPC).
[0036] The term "calcium-bearing starting material" refers to one
or more materials the chemical composition of which comprises Ca. A
calcium-bearing starting material can be a single material, such as
a mineral whose chemical composition includes the element Ca, such
as in the form of Ca cations as part of an ionic material, such as
a multinary metal oxide material. A calcium-bearing starting
material can be a plurality of materials, such as one or more
rocks, minerals, and/or industrially-processed material, wherein
the chemical composition of the combination of said plurality of
materials includes the element Ca, such as in the form of Ca
cations of an ionic material, such as a multinary metal oxide
material. Wherein a calcium-bearing starting material is a
plurality of materials, any one or any combination of said
plurality of materials can have a chemical composition comprising
the element Ca in order for the chemical composition of the
combination of said plurality of materials (which together are the
calcium-bearing starting material) to include the element Ca.
Preferably, a calcium-bearing starting material having a chemical
composition comprising the element Ca refers to the weight percent
and/or the molar percent of Ca in said calcium-bearing starting
material being at least 0.001%, preferably at least 0.01%,
preferably at least 0.1%, more preferably at least 1%, further more
preferably at least 5%, still more preferably at least 10%, and yet
more preferably at least 20%. On the other hand, the methods
disclosed herein are compatible with a calcium-bearing starting
material whose chemical composition has a low weight percent and/or
molar percent, such as less than 60%, less than 55%, less than 50%,
less than 45%, less than 40%, and less than 20%, at least because
Ca, along with respective counterions, can be isolated.
[0037] Generally, material or species having a chemical composition
characterized as comprising an element X (wherein "X" is an element
of the Periodic Table of Elements) refers to the weight percent
and/or the molar percent of X in said material or species being at
least 0.001%, preferably at least 0.01%, more preferably at least
0.1%, and still more preferably at least 1%.
[0038] The term "calcium salt" refers to a salt whose chemical
composition comprises the element Ca, for example in the form of Ca
cations. A salt is a chemical compound comprising ionic species
associated with each other at least in part via ionic bonding. For
example, CaSO.sub.4 and CaCl.sub.2) are calcium salts wherein Ca is
a cation and SO.sub.4 and CI, respectively, are anions.
[0039] A regeneration step refers to a step of a process for
producing a species or material using a product of a different step
that consumes (e.g., converted via chemical change into another
species or material) in said species or material. For example, a
reaction characterized by (A+B->C+D) consumes species A and B to
form species C and D. A reaction characterized by (C+E->A+F) can
be referred to as a regeneration reaction for regenerating species
A using a product (species C) of the reaction that consumed species
A.
[0040] The term "solid fraction" refers to solid species present in
a mixture of solid(s) and liquid(s). The term "liquid fraction"
refers to liquid species and species dissolved in the liquid
species in a mixture of solid(s) and liquid(s). For example, a
solid fraction can have the solid products of a chemical reaction
and liquid fraction can have the liquid and dissolved products of
the chemical reaction. Each of the solid fraction and the liquid
fraction can optionally include unreacted reagents. The liquid
fraction can include solvent(s) and ions dissolved in said
solvent(s).
[0041] A "dry mass" of one or more materials, such as a solid
fraction, refers to the mass of the one or more materials being
free of water, and optionally free of any liquid species.
[0042] The term "metal oxide" generally refers to a material whose
chemical composition comprises one or more metal elements and the
element O. Optionally, a metal oxide material is an ionic material
or at least partially an ionic material wherein at least a fraction
of the chemical bonding is characterized as ionic bonding. A metal
element is any metal element or metalloid element of the periodic
table of elements. Generally, a metalloid element is selected from
the group consisting of B, Si, Ge, As, Se, Sb, Te, Po, and At.
[0043] The term "natural rock or mineral" refers to one or more
materials that is naturally found in and has been extracted from
the Earth's crust. Natural rocks and minerals include, but are not
limited to, basalt, igneous appetites, wollastonite, anorthosite,
montmorillonite, bentonite, calcium-containing feldspar, anorthite,
diopside, pyroxene, pyroxenite, mafurite, kamafurite,
clinopyroxene, colemonite, grossular, augite, pigeonite, margarite,
calcium serpentine, garnet, scheilite, skarn, limestone, natural
gypsum, appetite, fluorapatite, and any combination of these. In
contrast, cement, concrete, Portland cements, fly ash, and slag are
not natural rocks or mineral but may be referred to as
industrially-derived materials.
[0044] The term "bulk acid" refers to an acid or acid solution that
does not require continuous input of energy (such as electrical
energy) and/or exchange of electrons with an electrode surface to
exist and function as required by a given process or step thereof.
In contrast, a heterogeneous or local acidic solution, such as of
hydronium ions or protons, near an electrode and formed as a result
of and substantially only during exchange of electrons between the
electrode and the solution is not a bulk acid. For example, a bulk
acid is not a heterogeneous or local or acidic solution
corresponding to a pH gradient formed at an electrode during water
electrolysis. In certain embodiments, the term "bulk acid" refers
to an acid or acid solution that exhibits thermodynamic, chemical,
and/or kinetic stability on a time scale of at least 10 seconds,
preferably at least 1 minute, in the absence of electrical energy
input. In certain embodiments, the term "bulk acid" refers to an
acid or acid solution that does exhibit or is capable of exhibiting
thermodynamic, chemical, and/or kinetic stability on a time scale
of at least 1 seconds and a length scale of at least 10 cm,
preferably at least 10 cm from a surface of a bulk material, in the
absence of electrical energy input.
[0045] The term "electrochemical cell" refers to devices and/or
device components that perform electrochemistry. Electrochemistry
refers to conversion of chemical energy into electrical energy or
electrical energy into chemical energy. Chemical energy can
correspond to a chemical change or chemical reaction.
Electrochemistry can thus refer to a chemical change (e.g., a
chemical reaction of one or more chemical species into one or more
other species) generating electrical energy and/or electrical
energy being converted into or used to induce a chemical change.
Electrical energy refers to electric potential energy,
corresponding to a combination of electric current and electric
potential in an electrical circuit. Electrochemical cells have two
or more electrodes (e.g., positive and negative electrodes; e.g.,
cathode and anode) and one or more electrolytes. An electrolyte may
include species that are oxidized and species that are reduced
during charging or discharging of the electrochemical cell.
Reactions occurring at the electrode, such as sorption and
desorption of a chemical species or such as an oxidation or
reduction reaction, contribute to charge transfer processes in the
electrochemical cell. Electrochemical cells include, but are not
limited to, electrolytic cells such as electrolysers and fuel
cells. Electrochemical oxidation may occur at the positive
electrode, for example, and electrochemical reduction may occur at
the negative electrode, for example. Electrochemical oxidation
refers to a chemical oxidation reaction accompanied by a transfer
of electrical energy (e.g., electrical energy input driving the
oxidation reaction) occurring in the context an electrochemical
cell. Similarly, electrochemical reduction refers to a chemical
reduction reaction accompanied by a transfer of electrical energy
occurring in the context an electrochemical cell. A chemical
species electrochemically oxidized during charging, for example,
may be electrochemically reduced during discharging, and vice
versa. The term "electrochemically" or "electrochemical" may
describe a reaction, process, or a step thereof, as part of which
chemical energy is converted into electrical energy or electrical
energy is converted into chemical energy. For example, a product
may be electrochemically formed when electrical energy is provided
to help the chemical conversion of a reactant(s) to the product
proceed. The term "non-electrochemical" refers to a reaction or
process that does not include electrochemistry and/or does not
require electrochemistry in order to be performed.
[0046] A reacting step refers to a process step wherein a chemical
reaction occurs, characterized by one or more chemical species
experiencing a chemical change (such as via chemically reacting
with each other) into another one or more chemical species.
[0047] The term "elemental sulfur" refers to any one or combination
of the allotropes of sulfur, such as, but not limited to, S7, S8,
S6, S12, and S18, and including crystalline, polycrystalline,
and/or amorphous sulfur.
[0048] "RHE" refers to the reference electrode commonly referred to
as the reversible hydrogen electrode. "SCE" refers to the reference
electrode commonly referred to as the saturated calomel
electrode.
[0049] The term "initial hours of operation" refers to the time
during which the cell is operational starting from the very
first/initial operation, or "turning on," of the cell. Time during
which the cell or system is not being operated (i.e., no
electrochemical reduction or oxidation occurring therein, or no
electrical energy input or output is occurring) is not included in
the initial hours of operation determination.
[0050] In some embodiments, the term "aqueous" refers to a solution
where the solvent is water such that other species of the solution,
or solutes, are substantially solvated by water. In some
embodiments, the term "aqueous" may generally refer to a solution
comprising water. Optionally, but not necessarily, an aqueous
solution or an aqueous solvent includes 5 vol. % or less of
non-aqueous solvent and/or solute species.
[0051] The term "amending agricultural water" refers to changing or
adding something, such as a solute, to agricultural water. For
example, acidification of agricultural water by the addition of
sulfuric acid, such as a solution including sulfuric acid, to
agricultural water. Agricultural water refers to water used for an
agricultural purpose, such as irrigation. The term "amending soil"
refers to changing or adding something to soil. For example,
acidification of soil by the addition of sulfuric acid, such as a
solution including sulfuric acid, to soil.
[0052] The term "cement" refers to hydraulic, non-hydraulic, or
both hydraulic and non-hydraulic cement material. An exemplary
cement is, but is not limited to, Portland cement. Generally, a
cement is a binder material, which, for example, may be mixed with
fine aggregate particles (such as to produce mortar for masonry) or
with sand and gravel (to produce concrete). According to certain
embodiments, cement comprises calcium oxide. Cement may optionally
further comprise one or more other materials including, but not
limited to, certain silicate(s), SiO.sub.2, certain oxide(s),
Fe.sub.2O.sub.3, certain aluminate(s), Al.sub.2O.sub.3, belite,
alite, tricalcium aluminate, brownmillerite, A "cement material"
refers to a material that is or can be a constituent of cement.
Preferably, a cement material has a chemical composition comprising
Ca or CaO. For example, CaO is a cement material. For example, a
cementitious material is a cement material. A composite cement
material may include a plurality of materials, including at least
one cement materials and optionally one or more additives.
Exemplary composite cement materials are, but are not limited to,
Portland cement clinker and Portland cement, such as Ordinary
Portland Cement (OPC).
[0053] The term "substantially" refers to a property or condition
that is within 20%, optionally within 10%, optionally within 5%,
optionally within 1%, or optionally is equivalent to a reference
property or condition. The term "substantially equal,"
"substantially equivalent," or "substantially unchanged," when used
in conjunction with a reference value describing a property or
condition, refers to a value or condition that is within 20%,
optionally within 10%, optionally within 5%, optionally within 1%,
optionally within 0.1%, or optionally is equivalent to the provided
reference value or condition. For example, a voltage that is
substantially 500 mV (or, substantially equivalent to 500 mV) is
within 20%, optionally within 10%, optionally within 5%, optionally
within 1%, or optionally equal to 500 mV. The term "substantially
greater," when used in conjunction with a reference value or
condition describing a property or condition, refers to a value
that is at least 2%, optionally at least 5%, optionally at least
10%, or optionally at least 20% greater than the provided reference
value or condition. For example, a voltage is substantially greater
than 500 mV if the voltage is at least 20% greater than, optionally
at least 10% greater than, optionally at least 5% greater than, or
optionally at least 1 greater than 500 mV. The term "substantially
less," when used in conjunction with a reference value or condition
describing a property or condition, refers to a value or condition
that is at least 2%, optionally at least 5%, optionally at least
10%, or optionally at least 20% less than the provided reference
value. For example, a voltage is substantially less than 500 mV if
the voltage is at least 20% less than, optionally at least 10% less
than, optionally at least 5% less than, or optionally at least 1%
less than 500 mV.
[0054] Further, incorporated herein by reference, to the extent not
inconsistent herewith, is U.S. Patent Publication No. 2019/0376191
(Finke; U.S. application Ser. No. 16/415,275), which may contain
additional useful terms, descriptions, and embodiments.
[0055] In an embodiment, a composition or compound of the
invention, such as an alloy or precursor to an alloy, is isolated
or substantially purified. In an embodiment, an isolated or
purified compound is at least partially isolated or substantially
purified as would be understood in the art. In an embodiment, a
substantially purified composition, compound or formulation of the
invention has a chemical purity of 95%, optionally for some
applications 99%, optionally for some applications 99.9%,
optionally for some applications 99.99%, and optionally for some
applications 99.999% pure.
DETAILED DESCRIPTION OF THE INVENTION
[0056] In the following description, numerous specific details of
the devices, device components and methods of the present invention
are set forth in order to provide a thorough explanation of the
precise nature of the invention. It will be apparent, however, to
those of skill in the art that the invention can be practiced
without these specific details.
[0057] The invention can be further understood by the following
non-limiting examples.
Example 1: A Process to Make Calcium Oxide or Ordinary Portland
Cement from Calcium Bearing Rocks and Minerals
[0058] Conventional cement is made by thermally decomposing
CaCO.sub.3 into CaO and then mixing it with other materials
including Al.sub.2Si.sub.2O.sub.5(OH).sub.4, Fe.sub.2O.sub.3, and
CaSO.sub.4. Thermal decomposition occurs at .about.900C and final
OPC production occurs at .about.1450C. Most of the energy required
and CO.sub.2 emissions for cement making come from the thermal
decomposition of limestone:
CaCO.sub.3.fwdarw.CaO+CO.sub.2.DELTA.H=178(non spontaneous)
(FX5).
[0059] Conventional cement requires 2.7-6 GJ/tonne OPC and produces
0.7-1.3 tonne CO.sub.2 per tonne of OPC (Ordinary Portland Cement).
The normal cement process emits a lot of CO.sub.2 and take a lot of
energy.
[0060] Included in this discloses is a process to produce CaO from
any calcium-bearing rock or mineral. In nature, acid (e.g.
H.sub.2CO.sub.3 or H.sub.2SO.sub.4) weathers calcium bearing
minerals to produce, typically, CaCO.sub.3 or CaSO.sub.4. The
general weathering trend follows:
H.sub.2CO.sub.3+CaAl.sub.2Si.sub.2O.sub.8+H.sub.2O.fwdarw.CaCO.sub.3+Al.-
sub.2Si.sub.2O.sub.5(OH).sub.4 (FX6);
or
H.sub.2SO.sub.4+CaAl.sub.2Si.sub.2O.sub.8+H.sub.2O.fwdarw.CaSO.sub.4+Al.-
sub.2Si.sub.2O.sub.5(OH).sub.4 (FX7).
[0061] In nature, these acids are very dilute and typically this
weathering occurs over long periods of time (weeks to decades).
Weathering can occur with a calcium bearing mineral or rock. Common
examples are wollastinite, anorthocite, Ca-bentonite,
montmorillonite, plagioclase and basalt. All calcium bearing rocks
are possible including all mafic and ultra-mafic rocks.
[0062] Methods disclosed herein can use an acid (e.g.
H.sub.2SO.sub.4, HF, HCl, H.sub.2CO.sub.3) or a combination of
acids plus a calcium bearing rock or mineral (e.g. anorthosite,
montmorillonite, wollastonite) to produce a calcium salt (e.g.
CaSO.sub.4, CaF.sub.2, CaCl.sub.2), CaCO.sub.3). It is then
possible to hydrate or thermally decompose this salt to produce
CaO. It may also be possible to achieve the correct ratios of
starting materials to thermally decompose the calcium salt and
byproducts into a cementitious material including Ordinary Portland
Cement or calcium sulfoaluminate cement. The strength,
concentration, or quality of the acid and the particle size of the
mined calcium-bearing rock can change the kinetics of the removal
of calcium salts from the calcium-bearing starting material and
different acid concentrations and crushed rock sizes may be optimal
for different versions of this process.
[0063] The advantages of the processes disclosed herein can include
that they can be CO.sub.2 free and energy neutral. For example:
H.sub.2SO.sub.4+CaAl.sub.2Si.sub.2O.sub.8+H.sub.2O.fwdarw.CaSO.sub.4+Al.-
sub.2Si.sub.2O.sub.5(OH).sub.4 (FX8);
CaSO.sub.4.fwdarw.CaO+SO.sub.2+1/2O.sub.2 (FX9);
SO.sub.2+H.sub.2O+1/2O.sub.2.fwdarw.H.sub.2SO.sub.4 (FX10);
Net:
CaAl.sub.2Si.sub.2O.sub.8+2H.sub.2O.fwdarw.CaO+Al.sub.2Si.sub.2O.su-
b.5(OH).sub.4 (FX11);
.DELTA.H=.about.0
[0064] This process could also be used to make clean hydrogen if
electrochemical cogeneration of H.sub.2 and H.sub.2SO.sub.4 are
used:
H.sub.2SO.sub.4+CaAl.sub.2Si.sub.2O.sub.8+H.sub.2O.fwdarw.CaSO.sub.4+Al.-
sub.2Si.sub.2O.sub.5(OH).sub.4 (FX12);
CaSO.sub.4.fwdarw.CaO+SO.sub.2+1/2O.sub.2 (FX13);
SO.sub.2+2H.sub.2O.fwdarw.H.sub.2+H.sub.2SO.sub.4 (FX14);
Net: CaAl.sub.2Si.sub.2O.sub.8+2H.sub.2O
.fwdarw.CaO+Al.sub.2Si.sub.2O.sub.5(OH).sub.4+'1/2O.sub.2+H.sub.2
(FX15);
.DELTA.H=50(slightly uphill)
Example 2: Reductive Thermal Decomposition of Limestone to Make
Lime or Cement
[0065] Lime is used directly as a commodity chemical as well as the
primary constituent of cement which is the most consumed human made
material on the planet. Lime is currently produced via the thermal
decomposition of limestone in an air atmosphere (FX16).
CaCO.sub.3.fwdarw.CO.sub.2+CaO (FX16);
This heat of decomposition of this reaction is 178 kJ/mol
[0066] Included in this invention is a process to produce cement
from limestone via reductive thermal decomposition with hydrogen.
The first step in the process may follow the following
reactions:
CaCO.sub.3+4H.sub.2.fwdarw.CH.sub.4+2H.sub.2O (FX17A);
or
CaCO.sub.3+2H.sub.2.fwdarw.CH.sub.4+O.sub.2(FX17B);
[0067] Water content of the reacting gas influences whether the
reaction proceeds according to FX17A, FX17B, or both. CaCO.sub.3
can react with H.sub.2 to either make CaO+CH.sub.4+O.sub.2 or
CaO+CH.sub.4+2H.sub.2O. If H.sub.2O is formed, 4H.sub.2s are
consumed. If O.sub.2 is formed, only 2H.sub.2s are consumed. This
reaction can be driven to only consume 2H.sub.2s if there is a
water atmosphere, for example.
[0068] The reaction may stop there or the second step may be
methane pyrolysis to regenerate the hydrogen, or any methane
involving chemical reaction:
CH.sub.4.fwdarw.2H.sub.2+C (FX18);
[0069] One benefit of this reaction is that we can make solid
carbon instead of CO.sub.2 and therefore will not pollute the
atmosphere. Another benefit of reaction FX17A is that it is a lower
energy requirement than traditional thermal decomposition of
limestone (13.1 kJ/mol). A benefit of reaction FX17B is that 100%
of the necessary hydrogen can be regenerated from methane
pyrolysis.
[0070] In certain embodiments, reaction FX17A occurs under reducing
conditions above 700C for example in an H.sub.2, an H.sub.2/N.sub.2
atmosphere or any other combination. Reaction FX17B may occur above
700C with H.sub.2 under a water atmosphere. For example, we put
2.011 g of CaCO.sub.3 powder into a tube furnace and heated it at
7C per minute. For example, we flowed forming gas at 0.3 liters per
minute (lpm). For example, we attached a gas analyzer to the back
of the furnace to measure the methane concentration. Data is found
in FIGS. 1 and 2. XPS is to determine that the resulting thermal
decomposition yielded >99% lime (FIG. 3).
[0071] By integrating under these curves, we determine that we
achieved .about.100% decarbonization.
Example 3: Production of Gypsum and Cement Materials
[0072] Exemplary aspect 1: The production of ordinary portland
cement (OPC) from any calcium containing starting material without
the net production of acid-forming gases (e.g. SO.sub.2 and
CO.sub.2). Examples of calcium containing starting materials
include: basalt, igneous appetites, wollastonite, slag, fly ash,
anorthosite, montmorillonite, bentonite, calcium-containing
feldspar, anorthite, diopside, pyroxene, pyroxenite, mafurite,
kamafurite, clinopyroxene, colemonite, grossular, augite,
pigeonite, margarite, calcium serpentine, garnet, scheilite, OPC,
concrete, any rock that has any Ca or CaO by mass especially rocks
with >5%, >10%, or >15% CaO, any skarns, limestone,
gypsum, appetite, or fluorapatite.
[0073] In certain embodiments, we do this by first producing
>90% pure synthetic gypsum from the above calcium containing
rocks (details in claim 2) and then thermally decomposing this
gypsum to make CaO and then mixing it with the proper ratios of
other materials to form OPC. The produced SO.sub.2 is then reformed
into sulfuric acid (via the contact process or via a sulfur
depolarization electrolyzer) which can then be recycled to make
synthetic gypsum. The general chemistry is below:
1. CaAl.sub.2Si.sub.2O.sub.8+H.sub.2SO.sub.4->CaSO.sub.4(>90
dry wt. % pure)+Al.sub.2O.sub.3+SiO.sub.2 (FX19);
2. CaSO.sub.4+heat->CaO+1/2O.sub.2+SO.sub.2 (FX20);
3. CaO+xAl.sub.2O.sub.3+ySiO.sub.2->OPC (FX21);
4. SO.sub.2+1/2O.sub.2+H.sub.2O->H.sub.2SO.sub.4 (FX22);
[0074] Ordinary Portland Cement (OPC) is made in industry today
exclusively from limestone (primarily CaCO.sub.3). The production
of OPC involves first producing CaO by thermally decomposing
CaCO.sub.3 (e.g. CaCO.sub.3+heat->CaO+CO.sub.2) and then heating
the CaO with silica and alumina to form OPC which is .about.60% CaO
by mass. The production of CO.sub.2 from cement manufacturing is
responsible for >5% of global CO.sub.2 emissions.
[0075] Besides limestone, OPC may also be made from gypsum
(CaSO.sub.4). Mined gypsum (CaSO.sub.4) can be used by some methods
for producing OPC. In this process CaSO.sub.4 is thermally
decomposed to produce CaO (e.g.
CaSO.sub.4+heat.fwdarw.CaO+1/2O.sub.2+SO.sub.2). This process can
also be accomplished with carbo or hydro thermic reduction in which
case CaS is produced by reacting CaSO.sub.4 with a reductant (e.g.
coal) and then CaS is co-thermally-decomposed with CaSO.sub.4 to
make CaO. This process is known as the Mueller-Kuehne Process.
Neither of these processes are practiced commercially today because
SO.sub.2 cannot be released into the atmosphere and the global
demand for SO.sub.2 is far lower than the demand for OPC.
[0076] OPC can be produced from "phosphogypsum" (CaSO.sub.4
produced by reacting phosphate rock with H.sub.2SO.sub.4 to make
phosphoric acid and gypsum). The fertilizer industry produces waste
CaSO.sub.4 by reacting sulfuric acid with phosphate rock (primarily
Ca.sub.5(PO.sub.4).sub.3OH) to make phosphoric acid. This synthetic
gypsum can be thermally decomposed to make CaO and then OPC as in
the process above.
[0077] Methods disclosed herein dramatically expand the starting
materials from which OPC can be made compared to conventional
methods.
[0078] Exemplary Aspect 2: The production of >90% purity
CaSO.sub.4 from any calcium containing rock. For example, HCl is
first reacted with the rock to dissolve the calcium chloride,
precipitates out >90 dry wt % purity SiO2, and other byproducts.
For example, we then react the dissolved solution with sulfuric
acid which selectively precipitates out CaSO.sub.4 as this is the
only sulfate salt among the common sulfate salts (MgSO.sub.4,
Al.sub.2(SO.sub.4).sub.3, Fe.sub.2(SO.sub.4).sub.3) that does not
dissolve in water. This also regenerates the HCl. Sample chemistry
is below:
1.
CaAl.sub.2Si.sub.2O.sub.8+O.sub.8HCl->CaCl.sub.2(aq)+2AlCl.sub.3(a-
q)+SO.sub.2(s) (FX23);
2. Separate the solid and aqueous fraction (FX24);
3.
CaCl.sub.2(aq)+2AlCl.sub.3(aq)+4H.sub.2SO.sub.4->CaSO.sub.4(s)+Al.-
sub.2(SO.sub.4).sub.3(aq)+8HCl (FX25);
[0079] Methods disclosed herein include production of >90 dry
wt. % purity CaSO.sub.4, which is make the process less expensive,
less complicated, more controllable of necessary materials ratios
for accurate production of OPC.
[0080] 90 dry wt. % calcium sulfate can also be produced as a
byproduct of reacting sulfuric acid with either limestone
(CaCO.sub.3) and phosphate rock (Ca.sub.5(PO.sub.4).sub.30H or
Ca.sub.5(PO.sub.4).sub.3F). The products of these reactions are
either water soluble (HF, H.sub.2PO.sub.4), liquid (H.sub.2O) or
gaseous (CO.sub.2).
[0081] Advantageously, methods disclosed herein can yield highly
pure synthetic gypsum from any rock even if the byproducts are not
soluble in sulfuric acid.
Example 4: Generation of valuable co-products
[0082] Exemplary aspect 3: The production of alumina from any
calcium containing rock. This can be done by first leaching with
HCl and then saturating the leach solution with HCl, the high HCl
concentration causes AlCl.sub.3 to precipitate. AlCl.sub.3 can then
be mixed with H.sub.2SO.sub.4 to make Al.sub.2(SO.sub.4).sub.3 and
regenerate the HCl. Al.sub.2(SO.sub.4).sub.3 can be thermally
decomposed to make Al.sub.2O.sub.3 and make SO.sub.2 in order to
regenerate the sulfuric acid. Exemplary chemistry below:
1.
CaAl.sub.2Si.sub.2O.sub.8+8HCl->CaCl.sub.2(aq)+2AlCl.sub.3(aq)+SiO-
.sub.2(s) (FX26);
2. AlCl.sub.3(aq)+HCl.sub.(aq)->Cl.sub.3(s)+HCl.sub.(aq)
(FX27);
3. 2AlCl.sub.3(s)+H.sub.2SO.sub.4->Al.sub.2(SO.sub.4).sub.3
(FX28);
4.
Al.sub.2(SO.sub.4).sub.3+heat->3SO.sub.2+Al.sub.2O.sub.3+3/2O.sub.-
2 (FX29);
5. SO.sub.2+1/2O.sub.2+H.sub.2O->H.sub.2SO.sub.4 (FX30);
[0083] Exemplary aspect 4: The production of iron oxide from any
calcium containing rock. Once Al, Ca, and Si are removed via the
process described above, only aqueous iron sulfate and magnesium
sulfate are left in solution. If the water is evaporated and the
salts are raised to 500-700C iron sulfate will decompose into
insoluble iron oxide and the remaining magnesium sulfate can be
dissolved away in water leaving only iron oxide.
[0084] Exemplary aspect 5: The production of supplementary
cementitious materials including silica fume from
calcium-containing rocks. A side benefit of our process is that
because it dissolves everything except the silica, the particle
size of everything is very small and therefore we can make
synthetic silica fume.
[0085] The production of value added co-products is a significant
advantage of methods disclosed herein. An unexpected added benefit
of the leach step(s), corresponding to the "first reacting" step,
or the reaction of a calcium-bearing starting material with a first
acid, is it can produce numerous co-products including
Al.sub.2O.sub.3, SiO.sub.2, silica-fume grade silica,
Fe.sub.2O.sub.3, and MgO. These products also may be highly pure
because a chemical separation is used. The use of HCl concentration
to precipitate aluminum had been used to make AlCl.sub.3 from
aluminum containing rocks but not to make Al.sub.2(SO.sub.4).sub.3,
as disclosed herein, according to certain embodiments, which has
the benefit of higher thermal decomposition efficiencies and the
regeneration of valuable HCl.
[0086] Methods disclosed herein include benefits of expanding the
starting materials that are capable of making these products, and,
in many cases, achieving better processes efficiencies, product
purities, and qualities than conventional processes.
STATEMENTS REGARDING INCORPORATION BY REFERENCE AND VARIATIONS
[0087] All references throughout this application, for example
patent documents including issued or granted patents or
equivalents; patent application publications; and non-patent
literature documents or other source material; are hereby
incorporated by reference herein in their entireties, as though
individually incorporated by reference, to the extent each
reference is at least partially not inconsistent with the
disclosure in this application (for example, a reference that is
partially inconsistent is incorporated by reference except for the
partially inconsistent portion of the reference).
[0088] The terms and expressions which have been employed herein
are used as terms of description and not of limitation, and there
is no intention in the use of such terms and expressions of
excluding any equivalents of the features shown and described or
portions thereof, but it is recognized that various modifications
are possible within the scope of the invention claimed. Thus, it
should be understood that although the present invention has been
specifically disclosed by preferred embodiments, exemplary
embodiments and optional features, modification and variation of
the concepts herein disclosed may be resorted to by those skilled
in the art, and that such modifications and variations are
considered to be within the scope of this invention as defined by
the appended claims. The specific embodiments provided herein are
examples of useful embodiments of the present invention and it will
be apparent to one skilled in the art that the present invention
may be carried out using a large number of variations of the
devices, device components, methods steps set forth in the present
description. As will be obvious to one of skill in the art, methods
and devices useful for the present methods can include a large
number of optional composition and processing elements and
steps.
[0089] As used herein and in the appended claims, the singular
forms "a", "an", and "the" include plural reference unless the
context clearly dictates otherwise. Thus, for example, reference to
"a cell" includes a plurality of such cells and equivalents thereof
known to those skilled in the art. As well, the terms "a" (or
"an"), "one or more" and "at least one" can be used interchangeably
herein. It is also to be noted that the terms "comprising",
"including", and "having" can be used interchangeably. The
expression "of any of claims XX-YY" (wherein XX and YY refer to
claim numbers) is intended to provide a multiple dependent claim in
the alternative form, and in some embodiments is interchangeable
with the expression "as in any one of claims XX-YY."
[0090] When a group of substituents is disclosed herein, it is
understood that all individual members of that group and all
subgroups, including any isomers, enantiomers, and diastereomers of
the group members, are disclosed separately. When a Markush group
or other grouping is used herein, all individual members of the
group and all combinations and subcombinations possible of the
group are intended to be individually included in the disclosure.
When a compound is described herein such that a particular isomer,
enantiomer or diastereomer of the compound is not specified, for
example, in a formula or in a chemical name, that description is
intended to include each isomers and enantiomer of the compound
described individual or in any combination. Additionally, unless
otherwise specified, all isotopic variants of compounds disclosed
herein are intended to be encompassed by the disclosure. For
example, it will be understood that any one or more hydrogens in a
molecule disclosed can be replaced with deuterium or tritium.
Isotopic variants of a molecule are generally useful as standards
in assays for the molecule and in chemical and biological research
related to the molecule or its use. Methods for making such
isotopic variants are known in the art. Specific names of compounds
are intended to be exemplary, as it is known that one of ordinary
skill in the art can name the same compounds differently.
[0091] Certain molecules disclosed herein may contain one or more
ionizable groups [groups from which a proton can be removed (e.g.,
--COOH) or added (e.g., amines) or which can be quaternized (e.g.,
amines)]. All possible ionic forms of such molecules and salts
thereof are intended to be included individually in the disclosure
herein. With regard to salts of the compounds herein, one of
ordinary skill in the art can select from among a wide variety of
available counterions those that are appropriate for preparation of
salts of this invention for a given application. In specific
applications, the selection of a given anion or cation for
preparation of a salt may result in increased or decreased
solubility of that salt.
[0092] Every device, system, formulation, composition, combination
of components, or method, or step thereof, described or exemplified
herein can be used to practice the invention, unless otherwise
stated.
[0093] Whenever a range is given in the specification, for example,
a temperature range, a time range, or a composition or
concentration range, all intermediate ranges and subranges, as well
as all individual values included in the ranges given are intended
to be included in the disclosure. It will be understood that any
subranges or individual values in a range or subrange that are
included in the description herein can be excluded from the claims
herein.
[0094] All patents and publications mentioned in the specification
are indicative of the levels of skill of those skilled in the art
to which the invention pertains. References cited herein are
incorporated by reference herein in their entirety to indicate the
state of the art as of their publication or filing date and it is
intended that this information can be employed herein, if needed,
to exclude specific embodiments that are in the prior art. For
example, when composition of matter are claimed, it should be
understood that compounds known and available in the art prior to
Applicant's invention, including compounds for which an enabling
disclosure is provided in the references cited herein, are not
intended to be included in the composition of matter claims
herein.
[0095] As used herein, "comprising" is synonymous with "including,"
"containing," or "characterized by," and is inclusive or open-ended
and does not exclude additional, unrecited elements or method
steps. As used herein, "consisting of" excludes any element, step,
or ingredient not specified in the claim element. As used herein,
"consisting essentially of" does not exclude materials or steps
that do not materially affect the basic and novel characteristics
of the claim. In each instance herein any of the terms
"comprising", "consisting essentially of" and "consisting of" may
be replaced with either of the other two terms. The invention
illustratively described herein suitably may be practiced in the
absence of any element or elements, limitation or limitations which
is not specifically disclosed herein.
[0096] One of ordinary skill in the art will appreciate that
starting materials, biological materials, reagents, synthetic
methods, purification methods, analytical methods, assay methods,
and biological methods other than those specifically exemplified
can be employed in the practice of the invention without resort to
undue experimentation. All art-known functional equivalents, of any
such materials and methods are intended to be included in this
invention. The terms and expressions which have been employed are
used as terms of description and not of limitation, and there is no
intention that in the use of such terms and expressions of
excluding any equivalents of the features shown and described or
portions thereof, but it is recognized that various modifications
are possible within the scope of the invention claimed. Thus, it
should be understood that although the present invention has been
specifically disclosed by preferred embodiments and optional
features, modification and variation of the concepts herein
disclosed may be resorted to by those skilled in the art, and that
such modifications and variations are considered to be within the
scope of this invention as defined by the appended claims.
* * * * *