Algae based biofertilizers production from the urea and / or ammonia plant wastewater and flue gas

Abstract

A method and a culture medium for culturing and growing algae utilizing a flue gas and wastewater from a urea plant and / or an ammonia plant are disclosed. In some instances, cultured algae is combined with one or more solid fertilizers to produce bio-fertilizers.

Description

DESCRIPTIONALGAE BASED BIOFERTILIZERS PRODUCTION FROM THE UREA AND / OR AMMONIA PLANT WASTEWATER AND FLUE GASCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to and the benefit of Indian Application No. 202441094533, filed November 29, 2024, the contents of which is incorporated into the present application in its entirety.BACKGROUND OF THE INVENTIONI. Field of the Disclosure

[0002] This disclosure generally concerns a method of culturing algae, and a production of biofertilizers from the same. In particular embodiments, the disclosure concerns a method of culturing and growing the algae in a culture medium comprising a flue gas and a wastewater from a urea plant and / or ammonia plant.II. Background

[0003] Carbon capture and / or storage is in growing demand worldwide as companies, industries, and countries are looking for ways to meet increasingly demanding regulations and environmental goals. Conventional Carbon Capture and Storage (CCS) technologies are not likely to meet these demands and goals. CCS technologies are faced with drawbacks such as high energy consumption, transportation difficulties, difficulties in meeting need of immediate utilization of captured carbon, and leakage of captured carbon to the atmosphere during storage. The primary requirements for algae cultivation are CO2, nutrients, sunlight and suitable temperature and pH. The fertilizer complex has all the ingredients required for the algal growth and the algal biomass is also a good sequestration option for carbon dioxide.

[0004] In particular, in ammonia and urea integrated fertilizer plants, the endothermic ammonia process as well as the heat needed to produce steam for the steam requirements for the urea process is often met by burning natural gas. Burning natural gas produces flue gases that contain in some instances 6 - 12 vol% CO2 that is, in some instances, vented to the atmosphere. There is a need to capture the CO2 that is emitted to the atmosphere from the flue gas. Further, waste water from the plants also contain CO2, in some instances 1 - 2.5 wt. % CO2, along with ammonia (2 - 5 wt. %) and urea (0.5 - 2 wt. %). This waste water is currently send to lagoons where they stay and can lose their CO2, as well as ammonia content, to the201777027.1 - 1 -atmosphere. There is a need to capture the wastewater CO2 and reduce the environmental impact of the wastewater .SUMMARY OF THE INVENTION

[0005] A solution to at least some of the problems discussed above is disclosed herein while also helping meet the growing demand for biofertilizers. The solution may reside in culturing algae utilizing flue gas and wastewater from a urea plant and / or ammonia plant. The algae converts the CO2 and nutrients in the wastewater and flue gas, such as ammonia and urea, into biomass. The biomass can be use in many ways, including as a fertilizer. The growing demand for fertilizers to help alleviate food production shortages can be at least partially met by use of the biomass or a derivative thereof, such as an extract, directly as a fertilizer or generating bio-fertilizer products by combining the biomass or derivative thereof with an additional nitrogen, phosphorous, and / or potassium (N, P, K, NP, NK, PK, or NPK) based fertilizer. In some aspects, the bio-fertilizer is produced so that the fertilizer has a slow-release characteristic for one or more of the nutrients therein.

[0006] In one aspect, a method of culturing algae is described herein. In some aspects, the method may comprise contacting algae with a culture medium that includes flue gas and wastewater from a urea plant and / or ammonia plant. In some aspects, the wastewater is from a urea plant. In some aspects, the algae is grown in a growth container with the culture medium. In some aspects, the growth container may be a reactor, a fermenter, a culture flask, a pond, a lake, and / or a lagoon. In some aspects, the wastewater from the plant may contain urea and / or ammonia. In some aspects, the wastewater contains ammonia. In some aspects, the wastewater contains 2 to 5 wt. % ammonia, such as at, greater than, less than, or between 2.0, 2.1, 2.2, 2.3,2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4,4.5, 4.6, 4.7, 4.8, 4.9, and 5 wt. % of ammonia, or any range thereof. In some aspects, the wastewater contains at, greater than, less than, or between 1 to 2.5 % of CO2, such as 1.0, 1.1,1.2, 1.3, 1.4, 1.5, 1.6, 1.7. 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, or 2.5 % of CO2, or any range thereof. In some aspects, the wastewater contains urea. In some aspects, the wastewater contains 0.5 to 2.0% urea, such as at, greater than, less than, or between 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2,1.3, 1.4, 1.5, 1.6, 1.7. 1.8, 1.9, or 2.0 % of urea, or any range thereof. In some aspects, the flue gas contains 8 to 10 vol. % of CO2, such as at, greater than, less than, or between 8.0, 8.1, 8.2,8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, or 10.0 vol. % of CO2, or any range thereof. In some aspects, the flue gas contains process gas. The process gas can contain 1 to 100 vol. % of CO2, such as at, greater than, less than, or between 1, 2, 3, 4, 5,201777027.1 - 2 -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, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56,57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81,82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100 vol. % of CO2or any range thereof. In some aspects, the algae may include a Chlorella species, a Nannochloris species, a Chlorogleopsis species, a Chlorocuccum species, and / or an Oscillatoria species.

[0007] In some aspects, the culture medium may further include an additional fertilizer other than urea and / or may further include a bacteria. In some aspects, the additional fertilizer may include ammonium sulfate and / or an iron-based fertilizer.

[0008] In some aspects, the method may further include pretreating the wastewater to remove at least a portion of solids and / or oils from the wastewater before contacting the flue gas and / or the algae. In some aspects, the method may further include diluting and / or cooling the flue gas before contacting the wastewater and / or the algae. In some aspects, the algae is grown at a temperature of 20°C to 50°C, such as, greater than, less than, or between 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, 46, 47, 48, 49, and 50°C, or any range therein. In some aspects, the algae growth may occur between 20 to 30° C, or between 30 to 40°C, or between 40 to 50° C, or any temperature between or range therein. In some aspects, the algae is grown at a pH of 4 to 9, such as at, greater than, less than, or between a pH of 9, 8, 7, 6, 5, or 4, any range therein.

[0009] In some aspects, the method further includes contacting the algae with light. In some aspects, the algae is grown in an incident light irradiance between 75 to 900 pmol photons / m2 / s, or at least any one of, equal to any one of, or between any two of 75, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310,320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500,510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690,700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880,890, and 900 pmol photons / m2 / s, or any range thereof. In some aspects, the algae is grown in a CO2concentration of the culture medium between 0.5% to 2% (v / v), or at least any one of, equal to any one of, or between any two of, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, and 2% (v / v), or any range thereof.

[0010] In some aspects, the method includes separating at least a portion of the algae. In some aspects, the method includes combining at least a portion of the separated algae with one or more solid fertilizers. In some aspects, the method includes drying at least a portion of the algae. In some aspects, the dried algae is combined with one or more solid fertilizers.201777027.1 - 3 -

[0011] In another aspect, a culture medium for culturing algae is described herein. In some aspects, the culture medium may include flue gas and wastewater from a urea plant and / or ammonia plant. In some aspects, the wastewater contains ammonia. In some aspects, the wastewater contains 2 to 5 wt. % ammonia, such as at, greater than, less than, or between 2.0,2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1,4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, and 5 wt. % of ammonia, or any range thereof. In some aspects, the wastewater contains at, greater than, less than, or between 1 to 2.5 % of CO2, such as 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7. 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, or 2.5 % of CO2, or any range thereof. In some aspects, the wastewater contains urea. In some aspects, the wastewater contains 0.5 to 2.0% urea, such as at, greater than, less than, or between 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7. 1.8, 1.9, or 2.0 % of urea, or any range thereof. In some aspects, the flue gas contains 8 to 10 vol. % of CO2, such as at, greater than, less than, or between 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, or 10.0 vol. % of CO2, or any range thereof. In some aspects, the flue gas contains process gas. The process gas can contain 1 to 100 vol. % of CO2, such as at, greater than, less than, or between 1, 2, 3, 4, 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, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100 vol. % of CO2 or any range thereof.

[0012] In some aspects, the culture medium may further include ammonium sulfate, ironbased fertilizers, and / or bacteria. In some aspects, the culture medium may further include micronutrients, vitamins, inorganic salts, and / or a pH adjuster.

[0013] Also disclosed are the following aspects 1 to 15 of the present invention.

[0014] Aspect 1 is a method of culturing algae, the method comprising: contacting algae with a culture medium, the culture medium comprising flue gas, and wastewater from a urea plant and / or ammonia plant; and growing the algae in a growth container with the culture medium.

[0015] Aspect 2 is the method of aspect 1, wherein the wastewater comprises urea and / or ammonia.

[0016] Aspect 3 is the method of any one of aspects 1 to 2, wherein the algae comprises Chlorella species, a Nannochloris species, a Chlorogleopsis species, a Chlorocuccum species, and / or Oscillatoria species.201777027.1 - 4 -

[0017] Aspect 4 is the method of any one of aspects 1 to 3, further comprising contacting the algae with light.

[0018] Aspect 5 is the method of any one of aspects 1 to 4, wherein the growth container is a reactor, a fermenter, a culture flask, a pond, a lake, and / or a lagoon.

[0019] Aspect 6 is the method of any one of aspects 1 to 5, further comprising separating at least a portion of the algae and / or drying at least a portion of the algae.

[0020] Aspect 7 is the method of any one of aspects 1 to 6, wherein the culture medium further comprises: an additional fertilizer other than urea; and / or a bacteria.

[0021] Aspect 8 is the method of aspect 7, wherein the additional fertilizer comprises ammonium sulfate and / or an iron-based fertilizer.

[0022] Aspect 9 is the method of any one of aspects 1 to 8, further comprising: pretreating the wastewater to remove at least a portion of solids and / or oils from the wastewater before contacting the flue gas; and / or diluting and / or cooling the flue gas before contacting the wastewater.

[0023] Aspect 10 is the method of any one of aspects 1 to 9, wherein the algae is grown at a temperature of 20°C to 50°C, at a pH of 4 to 9, in an incident light irradiance between 75 to 900 pmol photons / m2 / s, and / or in a CO2 concentration between 0.5% to 2% (v / v).

[0024] Aspect 11 is the method of any one of aspects 1 to 10, further comprising separating at least a portion of the algae and combining the at least a portion of the algae with one or more solid fertilizers.

[0025] Aspect 12 is a culture medium for culturing algae, the medium comprising: flue gas; and wastewater from a urea plant and / or wastewater from a ammonia plant.

[0026] Aspect 13 is the culture medium of aspect 12, wherein the wastewater comprises 2 to 5 wt. % ammonia, 1 to 2.5 % of CO2, and / or 0.5 to 2.0% urea; and / or wherein the flue gas comprises 8 to 10 vol. % of CO2.

[0027] Aspect 14 is the culture medium of any one of aspects 12 to 13, further comprising ammonium sulfate, an iron-based fertilizer, and / or bacteria.

[0028] Aspect 15 is the culture medium of any one of aspects 12 to 14, further comprising a micronutrient, a vitamin, an inorganic salt, and / or a pH adjuster.

[0029] The term “fertilizer” is defined as a material applied to soils or to plant tissues to supply one or more plant nutrients essential or beneficial to the growth of plants and / or stimulants or enhancers to increase or enhance plant growth.201777027.1 - 5 -

[0030] The term “granule” can include a solid material. A granule can have a variety of different shapes, non-limiting examples of which include a spherical, a puck, an oval, a rod, an oblong, or a random shape.

[0031] The term “particle” can include a solid material less than a millimeter in its largest dimension.

[0032] The terms “particulate” or “powder” can include a plurality of particles.

[0033] The terms “slow-release” and “slow release” fertilizers are fertilizer that release all of their plant nutrients over a period of weeks or more, instead of within a week or within hours.

[0034] The terms “about” or “approximately” as used herein are defined as being close to as understood by one of ordinary skill in the art. In one non-limiting embodiment, the terms are defined to be within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.

[0035] The terms “wt. %,” “vol.%,” or “mol.%” refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume of material, or total moles, that includes the component. In a non-limiting example, 10 grams of component in 100 grams of the material is 10 wt. % of component.

[0036] The use of the word “a” or “an” when used in conjunction with the term “comprising” may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.”

[0037] The phrase “and / or” means “and” or “or”. To illustrate, A, B, and / or C includes: A alone, B alone, C alone, a combination of A and B, a combination of A and C, a combination of B and C, or a combination of A, B, and C. In other words, “and / or” operates as an inclusive or.

[0038] The words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0039] The compositions and methods for their use can “comprise,” “consist essentially of,” or “consist of’ any of the ingredients or steps disclosed throughout the specification. Compositions and methods “consisting essentially of’ any of the ingredients or steps disclosed limits the scope of the claim to the specified materials or steps which do not materially affect the basic and novel characteristic of the claimed invention.201777027.1 - 6 -

[0040] It is contemplated that any embodiment discussed in this specification can be implemented with respect to any method or composition of the invention, and vice versa. Furthermore, compositions of the invention can be used to achieve methods of the invention.

[0041] Other objects, features and advantages of the present invention will become apparent from the following detailed description. It should be understood, however, that the detailed description and the specific examples, while indicating specific embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.BRIEF DESCRIPTION OF THE DRAWINGS

[0042] The following drawings form part of the present specification and are included to further demonstrate certain aspects of the present invention. The invention may be better understood by reference to one or more of these drawings in combination with the detailed description of specific embodiments presented herein.

[0043] FIG. 1 : a schematic of a method for culturing algae according to a non-limiting example of a culture medium and method disclosed herein.

[0044] FIG. 2: a schematic of a method for culturing algae according to another nonlimiting example of a culture medium and method disclosed herein.

[0045] FIG. 3 : a schematic of method for culturing algae according to another non-limiting example of a culture medium and method disclosed herein.DETAILED DESCRIPTION OF THE INVENTION

[0046] Certain aspects of the present disclosure provide benefits over existing methods for culturing algae, including culturing and growing an algae by utilizing a culture medium comprising a flue gas and wastewater from a urea plant and / or ammonia plant. In some aspects, bio-fertilizer products can be generated by combining the cultured algae with an additional nitrogen, phosphorous, and / or potassium based fertilizer. In some aspects, the algae is grown in the presence of the wastewater, the flue gas, and light. The algae may produce an algal biomass. The growth of the algal biomass sequesters CO2 and may minimize the CO2 emissions to the atmosphere of a plant that produces a flue gas and / or a wastewater. In some aspects, the algal biomass is used as a bio-fertilizer and / or is combined with additional fertilizers. In some aspects, the fertilizer has slow-release characteristics for a nutrient therein.201777027.1 - 7 -I. Culture Medium for Culturing Algae

[0047] In one aspect, a culture medium for culturing algae is described herein. In some aspects, the culture medium may include wastewater from a urea plant. In some aspects, the culture medium may include wastewater from an ammonium sulfate and / or ammonia plant. In some aspects, the culture medium may include flue gas. In some aspects, the flue gas may include CO2 such as process CO2. In some aspects, the flue gas may include CO2 from any industry.

[0048] In some aspects, the wastewater contains ammonia. In some aspects, the wastewater contains 2 to 5 wt. % ammonia, such as at, greater than, less than, or between 2.0, 2.1, 2.2, 2.3,2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4,4.5, 4.6, 4.7, 4.8, 4.9, and 5 wt. % of ammonia, or any range thereof. In some aspects, the wastewater contains at, greater than, less than, or between 1 to 2.5 % of CO2, such as 1.0, 1.1,1.2, 1.3, 1.4, 1.5, 1.6, 1.7. 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, or 2.5 % of CO2, or any range thereof. In some aspects, the wastewater contains urea. In some aspects, the wastewater contains 0.5 to 2.0% urea, such as at, greater than, less than, or between 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2,1.3, 1.4, 1.5, 1.6, 1.7. 1.8, 1.9, or 2.0 % of urea, or any range thereof. In some aspects, the flue gas contains 8 to 10 vol. % of CO2, such as at, greater than, less than, or between 8.0, 8.1, 8.2,8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, or 10.0 vol. % ofCO2, or any range thereof. In some aspects, the flue gas contains process gas. The process gas can contain 1 to 100 vol. % of CO2, such as at, greater than, less than, or between 1, 2, 3, 4, 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, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56,57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81,82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100 vol. % of CO2or any range thereof.

[0049] In some instances, the ammonia plant waste water may contain 400 to 1200 mg / L of ammonia, such as at, greater than, less than, or between 400, 500, 600, 700, 800, 900, 1000, 1100, or 1200 mg / L of ammonia, or any range thereof. In some instances, the ammonia plant waste water may contain 100 to 1200 mg / L of organics, such as at, greater than, less than, or between 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, or 1200 mg / L of organics; or any range thereof. In some instances, the organics are mainly methanol. In some instances, the ammonia plant waste water may contain 100 to 3000 mg / L of CO2 such as at, greater than, less than, or between 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300,201777027.1 - 8 -1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, or 3000 mg / L of CO2, or any range thereof.

[0050] In some aspects, the culture medium may further include ammonium sulfate. In some aspects, the culture medium may further include iron-based fertilizers such as ferrous sulfate, FeSO4 (such as at about 1% by wt. of the culture medium). In some aspects, the ironbased fertilizers may support and enhance the growth of algae, such as help the algae grow larger and / or store more carbon from the atmosphere. In some aspects, the culture medium may further include bacteria. In some aspects, synergy may occur by combining the algae with the bacteria, such as increased algae growth, reduced contamination in the growth medium and / or algal biomass, increased plant growth when applying the algal biomass or a derivative thereof to plants and / or soil and / or water for plants. In some aspects, the bacteria that promotes plant growth, such as a nitrogen fixing bacteria. In some aspects, the algae and bacteria symbiotic relationship may result in positive influence on each other’s physiological and metabolomic processes. In some aspects, combination of algae and bacteria may be expected to enhance shelf-life of a biofertilizer that contains the algal biomass or a derivative thereof.

[0051] In some aspects, the culture medium may contain mineral fertilizers like urea. In some aspects, the culture medium may further include a micronutrient, a vitamin, an inorganic salts, and / or a pH adjuster. In some aspects, the micronutrient, vitamin, inorganic salt, and / or pH adjuster is beneficial for the alga growth, the bacteria growth, or for plant growth when the algal biomass is applied to a plant, to a soil, and / or to water for a plant.II. Method of Culturing Algae

[0052] Referring to FIG. 1, a schematic of a system and method of culturing algae according to one example is described. The system 100 can include a urea plant / ammonia plant 102 and a growth container 104. In some aspects, algae 110 is contacted with a culture medium, where the culture medium may include wastewater 106 from a urea plant and / or ammonia plant 102 and flue gas and / or process gas 108. The algae 110 is grown in a growth container 104 with in the culture medium containing waste water 106 and flue gas and / or process gas 108. In some aspects, wastewater from the urea plant and / or ammonia plant 106 may include urea and ammonia.

[0053] Referring to FIG. 2 and FIG. 3, a schematic of a system and method 200 / 300 for culturing algae according to another two examples is described. In some aspects, the method may include contacting algae 210 / 310 with a culture medium. In some aspects, the culture medium may include flue gas and / or process gas 208 / 308 and wastewater 206 / 306 from a urea201777027.1 - 9 -plant 202 / 302 and / or wastewater 207 / 307 from an ammonia plant and / or ammonium sulfate plant 212 / 312. In some aspects, algae is grown in a growth container 204 / 304 with the culture medium. In some aspects, the wastewater 206 / 306 from the urea plant 202 / 302 may contain urea and ammonia. In some aspects, wastewater 207 / 307 from the ammonia plant or ammonium sulfate plant 212 / 312 may contain ammonia and / or ammonium sulfate. In some aspects, the method further may include contacting the algae 210 / 310 with light. In some aspects, the growth container 204 / 304 may be a reactor, a fermenter, a culture flask, a pond, a lake, and / or a lagoon. In some aspects, the method may further include separating at least a portion of the algae 311 from the growth container 304. In some aspects, the method may further include drying at least a portion of the separated algae in a dryer unit 314.

[0054] In some aspects, the urea plant 102 / 202 / 302 and / or ammonia plant 112 / 212 / 312 may circulate both the waste water (106 / 206 / 306 and / or 107 / 207 / 307) and flue gas 108 / 208 / 308 to the algae growth containers 104 / 204 / 304.

[0055] In some aspects, the culture medium may further includes an additional fertilizer other than urea and / or may include a bacteria. In some aspects, the additional fertilizer may include ammonium sulfate and / or an iron-based fertilizer. In some aspects, the method may further include pretreating the wastewater (206 / 306 and / or 207 / 307) to remove at least a portion of solids and / or oils from the wastewater before contacting the flue gas 208 / 308 and / or the algae 210 / 310. In some aspects, the method may further include diluting and / or cooling the flue gas 208 / 308 before contacting the wastewater (206 / 306 and / or 207 / 307) and / or the algae 210 / 310. In some aspects, water can be added to the culture medium.

[0056] In some aspects of the method, the algae may be grown at a temperature of 20°C to 50°C, such as at, greater than, less than, or between 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, 46, 47, 48, 49, and 50°C or any range thereof. In some aspects of the method, the algae growth may occur between 20 to 30° C, or between 30 to 40°C, or between 40 to 50° C, or any temperature between or range therein. In some aspects of the method, the algae may be grown at a pH of 4 to 9, such as at, greater than, less than, or between a pH of 4, 5, 6, 7, 8, 9, or any range thereof.

[0057] In some aspects of the method, the algae may be grown in the presence of light for at least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, or 24 hours per day. In some aspects of the method, the algae may be grown in an incident light irradiance between 75 to 900 pmol photons / m2 / s, or at least any one of, equal to any one of, or between any two of 75, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420,201777027.1 - 10 -430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, and 900 pmol photons / m2 / s or any range thereof. In some aspects of the method, the algae may be grown in a CO2 concentration between 0.5% to 2% (v / v), or at least any one of, equal to any one of, or between any two of, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, and 2% (v / v) or any range thereof.

[0058] In some aspects, the method may further includes separating at least a portion of the algae 311. In some aspects, the method may further includes combining at least a portion of the separated algae 311 with one or more solid fertilizers to prepare bio-fertilizers.

[0059] In some aspects, the prepared bio-fertilizers may contain 1 to 50 wt. % of separated algae or at least any one of, equal to any one of, or between any two of 1, 2, 3, 4, 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, 46, 47, 48, 49, and 50 wt. % of separated algae or any range thereof. In some aspects, the prepared bio-fertilizers may contain 50 to 99 wt. % of the solid fertilizer or at least any one of, equal to any one of, or between any two of 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, and 99 wt. % of the solid fertilizer or any range thereof. In some aspects, the solid fertilizer can be urea.

[0060] In some aspects, the produced bio-fertilizers may be further processed in a granulator. In some instances, the granulator can be a drum granulator, pugmill granulator, pan granulator, solid mixer, abrasion drum, extruder, high- shear mixer granulator, roller granulator, mycromix, or a round bottom flask. In the granulator, the algal biomass may be the entire or a portion of a feed mixture that can be granulated by agglomeration, spray granulation, compaction, slurry granulation and / or high- shear mixer granulation. In some particular aspect, the feed mixture can be granulated in the granulator by compaction. In some aspects, the granulator can contain at least two rollers and compaction granulation can include compressing the feed mixture using the at least two rollers. In some aspects, the two rollers can be moved in counter current direction during compaction. In some aspects, the feed mixture can be compressed into shaped pellets, such as cylindrical pellets, by the at least two rollers. In some aspects, a surface of one roller can have desired holes to compress the feed mixture into the holes, and the surface of the other roller can push the feed mixture into the holes. Pressure during granulation, e.g. compaction granulation can be 0.1 megapascal (MPa) to 4 MPa, or at least any one of, at most any one of, equal to any one of, or between any two 0.1, 0.2, 0.3, 0.4, 0.5, 1, 1.5, 2., 2.5, 3, 3.5, and 4 MPa. In certain aspects, the feed mixture can be granulated in201777027.1 - 11 -the granulator at ambient temperature to 50° C, or at least any one of, at most any one of, equal to any one of, or between any two of -20, -15, -10, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45 and 50° C.

[0061] In some aspects, contacting the culture medium ingredients such as wastewater and flue gas, and mixing those ingredients can be performed in a same container or in different containers. In some instances, the growth container may be more than one container according to the nature of chosen algae, such as the growth rate, rate of photosynthesis, temperature tolerance, and / or tolerance to trace constituent of gases such as NOx, Sox, and gaseous hydrocarbons.

[0062] In some aspects, the algal biomass is formed at a temperature of at least, at most, equal to, or between any two of 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, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, or 75° C, such as between 20 and 30° C or between 20 and 50° C or between 50 and 70° C or between 55 to 75° C.

[0063] In some embodiments, the algae can be cultured and / or concentrated to greater than, or equal to, approximately IxlO4to IxlO13colony forming units (CFU) per mL prior to addition to a composition or in a composition, such as a fertilizer, or before being dried. In some embodiments, the algae can be cultured and / or concentrated to greater than, or equal to, approximately IxlO4, IxlO5, IxlO6, IxlO7, IxlO8, IxlO9, IxlO10, IxlO11, IxlO12, IxlO13CFU per mL. In some embodiments, the algae can be cultured and / or concentrated to greater than, or equal to, approximately IxlO5to IxlO10, IxlO6to IxlO10, IxlO7to IxlO10, IxlO8to IxlO10, IxlO5to IxlO9, IxlO5to IxlO8, IxlO6to IxlO9, IxlO6to IxlO8, or IxlO8to IxlO9CFU per mL prior to addition to the composition or in the composition.

[0064] In some instances, the bio -fertilizer can be extruded before drying. The extruder can extrude the fertilizer at pressures at least, at most, equal to, or between any two of 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and 1 Mpa. The extruder can extrude the bio-fertilizer at temperatures at least, at most, equal to, or between any two of -20, -15, -10, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45 and 50° C. The extrudate can be sliced or divided before drying, such as by a die.

[0065] In certain aspects, the desired size of a final bio-fertilizer product, such as a granule, can be 0.5 to 5 mm, or 1 to 4 mm, and having a size lower than 0.5 mm or 1 mm, and / or having a size bigger than 4 mm or 5 mm can be separated from the wet granulated mixture in the one or more size screens. In certain aspects, the wet granulated mixture can be rounded and / or spheronized in a spheronizer. In some instances, the wet granulated mixture is contacted with a spheronizer for at least any one of, at most any one of, equal to any one of, or between any201777027.1 - 12 -two of 5, 10, 15, 20, 25, 30, 35, 40, 50, or 60 seconds. The spheronizer in some instances has a rotating or rotatable disk capable of rotating at least any one of, at most any one of, equal to any one of, or between any two of 200, 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000 rpm. In certain aspects, the wet granulated mixture can be dried in the dryer 314 at a temperature 40° C to 150° C, or at least any one of, at most any one of, equal to any one of, or between any two of 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150° C. In some aspects, the dryer 304 can be a fluid bed dryer, drum dryer, or flash dryer. In some aspects, the wet granulated mixture can be dried in the dryer 304 with an hot air flow having a flow rate of at least any one of, at most any one of, equal to any one of, or between any two of 100, 150, 200, 250, 300, 350, 400, 450, and 500 m3 / hr and / or a rotation of at least any one of, at most any one of, equal to any one of, or between any two of 5, 10, 15, 20, 25, 30, 35, 40, 45, and 50 rpm.III. Algae and Bacteria

[0066] Algae that may be used include, but are not limited to the following: a Chlorella species; a Nannochloris species; a Chlorogleopsis species; a Chlorocuccum species; and / or an Oscillatoria species.

[0067] In some aspects, the algae that may be used includes, but is not limited to, an algae species from the following genera: Acetabularia, Chlamydomonas, Chlorella, Cladophora, Codium, Hydrodictyon, Oedogonium, Pediastrum, Pleurococcus, Scenedesmus, Spirogyra, Ulothrix, Ulva, Volvox, Ceratium, Gonyaulax, Gymnodinium, Noctiluca, Peridinium, Euglena, Batrachospermum, Callophyllis, Porphyra, and / or Nitophyllum.

[0068] Bacteria that may be used include, but are not limited to the following: nitrogen fixing bacteria; potassium solubilizing bacteria; and / or phosphorus solubilizing bacteria. In some aspects, the nitrogen fixing bacteria comprises Methylobacterium aminovorans, Methylobacterium radiotolerans, Azotobacter chroococcum and! or Azo spirillum brasilense. In some aspects, the potassium solubilizing bacteria comprises Bacillus mucilaginosus and / or Uraturia aurantia. In some aspects, the phosphorus solubilizing bacteria comprises Bacillus megaterium var. phosphaticum, Paenibacillus polymyxa, and / or Bacillus subtilis. In some aspects, the bacteria is a diazotrophic bacteria, Azospirillum species, Azotobacter species, Frateuria aurantia, Bacillus species, endophytes, nitrogen fixing bacteria, methylotrophs, comammox (e.g., (COMplete AMMonia Oxidation) an organism that can convert ammonia into nitrite and then into nitrate through the process of nitrification), phosphorus solubilizing,201777027.1 - 13 -nitrite oxidizing, Nitrospira species, Methylobacterium species, and / or pink pigmented facultative methylotrophs (PPFM-trophs).IV. Methods of Using the Cultured Algae

[0069] The algae produced in the methods herein may be used as a fertilizer, animal feed, for production of a syn gas (such as by gasification), for production of bio-fuels such as biodiesel by pyrolysis, for harvesting other products such as oils, proteins, polysaccharides, etc., for storing carbon (such as burying to store) or other uses that are known in the art. In some instances, a bio-fertilizer may be produced by combining at least a portion of the separated cultured algae with one or more solid fertilizers. The algae biomass may be included in fertilizer granules, compositions containing a fertilizer, and fertilizer blends. The fertilizer may be used in methods of increasing the amount of one or more plant nutrients in soil and / or of enhancing plant growth. Such methods can include applying to the soil an effective amount of a composition and / or blend containing the bio-fertilizer of the present invention. The method may include increasing the growth and yield of crops, trees, ornamentals, etc., such as, for example, palm, coconut, rice, wheat, corn, barley, oats, and / or soybeans. The method can include applying the bio-fertilizer blend of the present invention to at least one of a soil, an organism, a liquid carrier, a liquid solvent, etc. The composition(s) and / or fertilizer blends(s) containing the bio-fertilizer can be applied to plants and / or soil as a top dressing fertilizer, basal fertilizer, and / or through any suitable method of application.

[0070] In some aspects, the algae is contacted with the fertilizer at a concentration of that provides 0.0001 to 98 wt. % algae per weight of the fertilizer, such as at, greater than, less than, or between 0.0001, 0.0002, 0.0003, 0.0004, 0.0005, 0.0006, 0.0007, 0.0008, 0.0009, 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 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, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65,66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90,91, 92, 93, 94, 95, 96, 97, or 98 wt. % algae per weight of the fertilizer, or any range thereof. In some aspects, the algae is comprised in a liquid, suspension, and / or dried powder.

[0071] Non-limiting examples of the bio-fertilizers that can be derived from the integrated process may use in direct application of the biomass. In some aspects, the biomass is applied in arid cultivation. In some aspects, the biomass can provide a carbon source for the soil and / or plants. In some instances, the algae may be sun-dried to a point where no further biological201777027.1 - 14 -degradation can occur. In some instances, the dried mass can be buried a few meters below the surface ensuring its stability for many centuries to lock sequestered carbon. In some instances, algae mass may also be buried in sea-beds where too, it can stay for centuries locking sequestered carbon. In some instances, wet algae biomass without dewatering can be directly fed as biofertilizer to the plants. In some instances, wet algae without dewatering can be mixed with the ammonium sulphate or any nutrients in soluble form and can be used as fertilizer enriched bio fertilizer. In some instances, concentrated wet algae can be composted with urea or other fertilizers and can be used as humus fertilizer. In some instances, dry algal biomass can be mixed with urea or other fertilizer and can be compacted into granules and applied as fertilizer. In some instances, CO2 enriched ammonium sulphate solution can be used as foliar fertilizer. In some instances, algae may be further converted to other value-added products for non-fertilizer applications like animal feed, nutraceuticals, biofuels, bio-oil, biochar etc..

[0072] Non-limiting examples of plants that can benefit from the bio-fertilizer of the present invention include vines, trees, shrubs, stalked plants, ferns, etc. The plants may include orchard crops, vines, ornamental plants, food crops, timber, and harvested plants. The plants may include Gymnosperms, Angiosperms, and / or Pteridophytes.

[0073] The effectiveness of compositions comprising the bio-fertilizer of the present invention can be ascertained by measuring the amount of one or more nutrients in the soil at various times after applying the fertilizer composition to the soil. It is understood that different soils have different characteristics, which can affect the stability of the nutrients in the soil. The effectiveness of a fertilizer composition can also be directly compared to other fertilizer compositions by doing a side-by-side comparison in the same soil under the same conditions.EXAMPLES

[0074] The present invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes only, and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of noncritical parameters which can be changed or modified to yield essentially the same results.Prophetic Example 1 Culture of an Algae

[0075] The growth conditions such as culture medium, pH tolerance, and temperature tolerance may be optimized for culturing a chosen algae. Algae species will be tested for growth in a culture medium containing wastewater from a urea plant and / or a ammonium plant and201777027.1 - 15 -flue gas. In some aspects, compositions of wastewater and flue gas use in the culture medium are depicted in Tables 1 and 2.Table 1 - Flue gas compositionTable 2 - Wastewater composition will be tested in the culture medium t6.

[0076] In some aspects, the waste water can be stripped of mechanical debris and other contaminants, such as oil, and will be fed to the growth container, such as an algal pond / algae reactor. The flue gas from the plant can also be cooled and fed into the pond / reactor through diffusers. In some instances, flue gas can be processed prior to fed into the growth container. Process CO2 emissions can further be diluted with the flue gas before injection if needed to regulate the amount of CO2 in the growth medium.

[0077] In some aspects, an another alternative approach can be the use of the CO2 absorbed in the waste water or the ammonium sulphate solution (this solution is derived from the various strippers that uses sulfuric acid to strip off ammonia from the stripper and is send to recover the ammonium sulphate from the solution) that can also be fed to the growth container as nutrients. Under the right nutrients and CO2 conditions, in the presence of light, the algae may multiply and form an algal biomass. Growth results that may be significantly different for different algae cultured. The algal biomass can in some aspects ensures that the CO2 is sequestered and hence the credit for the corresponding CO2 can be obtained. In some instances, at least some part of the obtained cultured algae can be separated and dried. In some instances, at least a portion of the separated wet and / or dry algae can be combined with the at least a portion of the one or more solid fertilizers to generate some bio-fertilizers.

[0078] In some instances, the cultured algae can be a good source of carbon as well as a good fertilizer. It has been determined that, 1.8 ton of CO2 is needed to grow 1 ton of algal biomass.201777027.1 - 16 -

[0079] All of the methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the invention. More specifically, it will be apparent that certain agents which are both chemically and physiologically related may be substituted for the agents described herein while the same or similar results would be achieved. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the appended claims.201777027.1 - 17 -

Claims

1. WHAT IS CLAIMED IS:

1. A method of culturing algae, the method comprising: contacting algae with a culture medium, the culture medium comprising a flue gas, and wastewater from a urea plant and / or ammonia plant; and growing the algae in a growth container with the culture medium.

2. The method of claim 1, wherein the wastewater comprises urea and ammonia.

3. The method of any one of claims 1 to 2, wherein the algae comprises Chlorella species and / or Oscillatoria species.

4. The method of any one of claims 1 to 3, further comprising contacting the algae with light.

5. The method of any one of claims 1 to 4, wherein the growth container is a reactor, a fermenter, a culture flask, a pond, a lake, and / or a lagoon.

6. The method of any one of claims 1 to 5, further comprising separating at least a portion of the algae and / or drying at least a portion of the algae.

7. The method of any one of claims 1 to 6, wherein the culture medium further comprises: an additional fertilizer other than urea; and / or a bacteria.

8. The method of claim 7, wherein the additional fertilizer comprises ammonium sulfate and / or an iron-based fertilizer.

9. The method of any one of claims 1 to 8, further comprising: pretreating the wastewater to remove at least a portion of solids and / or oils from the wastewater before contacting the flue gas; and / or diluting and / or cooling the flue gas before contacting the wastewater.201777027.1 - 18 -10. The method of any one of claims 1 to 9, wherein the algae is grown at a temperature of 20°C to 50°C, at a pH of 4 to 9, in an incident light irradiance between 75 to 900 pmol photons / m2 / s, and / or in a CO2 concentration between 0.5% to 2% (v / v).

11. The method of any one of claims 1 to 10, further comprising separating at least a portion of the algae and combining the at least a portion of the algae with one or more solid fertilizers.

12. A culture medium for culturing algae, the medium comprising: wastewater from a urea plant and / or ammonia plant; and flue gas.

13. The culture medium of claim 12, wherein the wastewater comprises 2 to 5 wt. % ammonia, 1 to 2.5 % of CO2, and 0.5 to 2,0% urea; and / or wherein the flue gas comprises 8 to 10 vol. % of CO2.

14. The culture medium of any one of claims 12 to 13, further comprising ammonium sulfate, an iron-based fertilizer, and / or bacteria.

15. The culture medium of any one of claims 12 to 14, further comprising a micronutrient, a vitamin, an inorganic salt, and / or a pH adjuster.201777027.1 - 19 -