EP3177383A1 - Method for upgrading biogas and production of ammonium sulphate - Google Patents

Method for upgrading biogas and production of ammonium sulphate

Info

Publication number
EP3177383A1
EP3177383A1 EP15736839.0A EP15736839A EP3177383A1 EP 3177383 A1 EP3177383 A1 EP 3177383A1 EP 15736839 A EP15736839 A EP 15736839A EP 3177383 A1 EP3177383 A1 EP 3177383A1
Authority
EP
European Patent Office
Prior art keywords
biogas
molecular sieve
hydrogen sulfide
conduit
produce
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP15736839.0A
Other languages
German (de)
French (fr)
Inventor
Jan Piet Warnar
Petronella Wilhelmina WARNAR
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Airpack Holding BV
Original Assignee
Airpack Holding BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Airpack Holding BV filed Critical Airpack Holding BV
Publication of EP3177383A1 publication Critical patent/EP3177383A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/26—Drying gases or vapours
    • B01D53/265—Drying gases or vapours by refrigeration (condensation)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/24—Sulfates of ammonium
    • C01C1/242—Preparation from ammonia and sulfuric acid or sulfur trioxide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • C10L3/103—Sulfur containing contaminants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/106—Removal of contaminants of water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/10—Oxidants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2062—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/24—Hydrocarbons
    • B01D2256/245—Methane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/304—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/05—Biogas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40011—Methods relating to the process cycle in pressure or temperature swing adsorption
    • B01D2259/40043—Purging
    • B01D2259/4005—Nature of purge gas
    • B01D2259/40052—Recycled product or process gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
    • B01D2259/40088—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/402—Further details for adsorption processes and devices using two beds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/414—Further details for adsorption processes and devices using different types of adsorbents
    • B01D2259/4141—Further details for adsorption processes and devices using different types of adsorbents within a single bed
    • B01D2259/4145—Further details for adsorption processes and devices using different types of adsorbents within a single bed arranged in series
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/0462—Temperature swing adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/52—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/73—After-treatment of removed components
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/06—Heat exchange, direct or indirect
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/12—Regeneration of a solvent, catalyst, adsorbent or any other component used to treat or prepare a fuel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/24—Mixing, stirring of fuel components
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/46—Compressors or pumps
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C10L2290/541—Absorption of impurities during preparation or upgrading of a fuel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C10L2290/542—Adsorption of impurities during preparation or upgrading of a fuel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C10L2290/545—Washing, scrubbing, stripping, scavenging for separating fractions, components or impurities during preparation or upgrading of a fuel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/08—Production of synthetic natural gas
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M47/00—Means for after-treatment of the produced biomass or of the fermentation or metabolic products, e.g. storage of biomass
    • C12M47/18—Gas cleaning, e.g. scrubbers; Separation of different gases
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

Definitions

  • the present invention relates according to a first aspect to a method for upgrading biogas and production of ammonium sulphate. According to another aspect the present invention relates to a system suitable for upgrading biogas and production of ammonium sulphate.
  • Biogas is produced by anaerobic digestion with anaerobic bacteria or by fermentation of biodegradable materials such as manure, sewage, municipal waste, green waste, plant material etc.
  • Biogas generally comprises methane, carbon dioxide, and small amounts of hydrogen sulfide, also known as H 2 S.
  • the methane can be combusted with oxygen and allows biogas to be used as a fuel.
  • biogas is suitable to be used as fuel, it is commonly upgraded to concentrate the methane.
  • the hydrogen sulfide which is present in biogas has a highly corrosive nature and may destroy the internals of a plant.
  • Common upgrading methods aim to separate the hydrogen sulfide from the biogas.
  • the concentrated hydrogen sulfide raises another problem because hydrogen sulfide is an undesired by product in view of its toxicity, flammability and corrosiveness.
  • Hydrogen sulfide is difficult to store, and especially for farmers having their own digesters for biomass.
  • the main way to convert hydrogen sulfide is the Claus process, in which the hydrogen sulfide reacts with sulfur dioxide at high temperature and/or in presence of a catalyst.
  • the disadvantage of the Claus process is that multi steps are required, i.e. both a thermal and a catalytic step, to convert the hydrogen sulfide to water and sulfur. Further, the disadvantage of the Claus process is that it would be difficult to perform for farmers having their own digesters for biomass.
  • this objective is met by providing a method for upgrading biogas and /or for the production of ammonium sulphate, comprising the steps of :
  • the present inventors surprisingly found that the method enables the removal of hydrogen sulfide from biogas provided from a digester, wherein the amount of hydrogen sulfide in the final pseudo gas is less than 1 percent of the initial hydrogen sulfide concentration in the biogas.
  • the sulfur component of the hydrogen sulfide advantageously could be used for the production of ammonium sulphate.
  • ammonia provides an undesired pungent smell.
  • the farmer is able to convert this ammonia to ammonium sulphate, which is furthermore advantageous because ammonium sulphate is a common used fertilizer for lowering the pH of the soil while contributing essential nitrogen for plant growth.
  • the water content of the biogas is reduced to a water content of less than 10 % (w/w), less than 5% (w/w) or less than 1% (w/w) of the amount of water which is present before condensing.
  • the advantage of reducing the amount of water is that the formation of sulphuric acid and/or formic acid is avoided. Both acids may be formed during processing and are very damaging for the downstream process equipment, such as a compressor.
  • the biogas which may be condensed in the present step (i) may be any biogas obtained from a digester.
  • a biogas has a temperature of 35°C to 45°C and comprises about 75% methane and 25 carbon dioxide, as well as trace elements hydrogen sulfide.
  • the present biogas of step (i) is wet biogas directly obtained from digesters and/or comprises about 10,000 ppm hydrogen sulfide.
  • the biogas with a reduced water content is pressurized to a pressure of at least 5 bar, such as 5 to 50 bar, 5 to 25 bar, preferably 6 to 15, more preferably 6 to 10 bar to produce pressurized biogas.
  • the advantage of pressurizing the biogas with reduced water content is that a more efficient sieving of hydrogen sulfide is obtained, providing the production of pseudo gas with substantially no hydrogen sulfide.
  • present step (iii) leading the pressurized biogas over a molecular sieve to separate hydrogen sulfide and to produce pseudo gas preferably separates hydrogen sulfide with a concentration of at least 50.000 ppm.
  • the present step (iv) of leading the separated hydrogen sulfide to an incinerator / quencher and heating the hydrogen sulfide to a temperature above 700°C and quenching the heated hydrogen sulfide with water to produce sulphuric acid preferably comprises heating the hydrogen sulfide to a temperature within the range of 700°C to 800°C.
  • the present method comprises leading a portion of the produced pseudo gas over the molecular sieve to regenerate the molecular sieve to separate the water and/or hydrogen sulfide from the molecular sieve , while simultaneously leading the pressurized biogas over a second, or third, molecular sieve to produce pseudo gas.
  • Pseudo gas, or alternatively purified biogas as used in the present context means biogas with a reduced hydrogen sulfide content, s.
  • Leading a portion of the produced pseudo gas, such as from 1 to 15% of the produced pseudo gas, over the molecular sieve regenerates the sieve by separating the concentrated water and hydrogen sulfide from the sieve. It is advantageous to simultaneously use a second, or further, molecular sieve to continue the production of pseudo gas while the molecular sieve is regenerating since a continuous process is provided.
  • the present molecular sieves are regenerated by leading a portion of the produced pseudo gas first of the second part of the molecular sieve, and subsequently leading the pseudo gas over the first part of the molecular sieve.
  • the present step (iv) of leading the separated hydrogen sulfide to an incinerator / quencher and heating the hydrogen sulfide to a temperature above 700°C and quenching the heated hydrogen sulfide with water to produce sulphuric acid preferably comprises leading the separated hydrogen sulfide via a regeneration flow of produced pseudo gas over the respective molecular sieve.
  • the present molecular sieve is heated during the regeneration of the molecular sieve, preferably to a temperature within the range of 150°C to 500°C, more preferably 200°C to 400°C.
  • the molecular sieve is heated with heat derived from the present incinerator / quencher.
  • the present method comprises leading the pressurized biogas over a first part of the molecular sieve having a diameter of less than 4 A, preferably less than 3.5 A or from 2.5 A to 3.5 A, to separate water and/or comprising leading the pressurized biogas over a second part of the molecular sieve having a diameter of less than 6 A, preferably less than 5.5 A or from 4.5 A to 5.5 A, to separate hydrogen sulfide.
  • the present pressurized biogas is first led over the first part of the molecular sieve and subsequently led over the second part of the molecular sieve.
  • the present method comprises mixing the pseudo gas in a mixing vessel to obtain pseudo gas having a uniform composition.
  • the present process is a continuous process, but the composition of the produced pseudo gas fluctuates during the process.
  • the fluctuations in the composition are minimalized. This is advantageous since the uniform pseudo gas could easier be used in combustion applications.
  • the present the pseudo gas or uniform pseudo gas comprises less than 100 ppm, more preferably less than 50 ppm hydrogen sulfide.
  • the present biogas derived from a digester is brought to a pressure of 20 to 100 mbar, preferably 40 to 60 mbar, before the biogas is condensed in step (i).
  • This pressure provides a more efficient reduction of water and thus the risk of damage of corrosive sulphuric acid or formic acid is reduced.
  • the biogas is supplied from a supply source, such as a digester, by using an under pressure, providing that the biogas is easily transferred to the condenser.
  • the present cooling medium has a temperature within the range of 10°C to 25°C, preferably 15°C to 20°C.
  • the present cooling medium is water; however another cooling medium may also be used.
  • the present invention relates to a system suitable for upgrading biogas and/or production of ammonium sulphate, comprising, a conduit for the supply of biogas which is connected to a cooler and/or a condenser, the condenser is further connected via a conduit to a compressor suitable to pressurize a gas stream to 5 to 25 bar, which compressor is connected via a conduit to a first inlet of a molecular sieve, which molecular sieve is preferably connected via a first outlet and conduit with a mixing vessel, and preferably with a second outlet with an incinerator / quencher, which incinerator / quencher is connected via a conduit with an acid water tank.
  • the system according to the present invention is a compact system that conveniently can be connected with digesters.
  • the present system provides upgrading of the biogas from the digester, while simultaneously hydrogen sulfide separated from the biogas is used for the production of ammonium sulphate.
  • the present invention provides an easy and efficient onsite system for the production of both ammonium sulphate and pseudo gas, or purified biogas.
  • the present compressor is connected with a further first inlet of a second molecular sieve, which second molecular sieve is connected via a first outlet and conduit with the mixing vessel. Accordingly, the first and second molecular sieves are situated in parallel between the compressor and the mixing vessel. This provides the advantage that the second molecular sieve can be used for separating water and/or hydrogen sulfide from the pressurized biogas while the first molecular sieve will be regenerated, and vice versa.
  • the conduit between the first outlet and the mixing vessel is connected another conduit connecting to the mixing vessel, enabling backflow of pseudo gas from the mixing vessel to the first outlet of the molecular sieve.
  • This backflow of pseudo gas from the mixing vessel towards the first or second molecular sieve provides regeneration of the respective molecular sieve by separating the concentrated water and/or hydrogen sulfide from the molecular sieve. Furthermore, this backflow leads the concentrated hydrogen sulfide towards the present incinerator / quencher.
  • the present molecular sieve comprises a first part having a sieve diameter of less than 4 A, preferably less than 3.5 A or from 2.5 A to 3.5 A, to separate water and/or comprising leading the pressurized biogas over a second part of the molecular sieve having a diameter of less than 6 A, preferably less than 5.5 A or from 4.5 A to 5.5 A to separate hydrogen sulfide.
  • the second part is connected to the first outlet of the molecular sieve.
  • the present molecular sieve is provided with heating means configured to heat the sieve to a temperature within the range of 150°C to 500°C.
  • the heating means derive heat from the present incinerator / quencher.
  • the present conduit for the supply of biogas is provided with a compressor configured to bring the biogas to a pressure of 20 to 100 mbar.
  • figure 1 shows a conduit 11 for the supply of biogas from a digester.
  • Conduit 11 is preferably provided with suitable valves to regulate the flow of biogas.
  • conduit 11 is provided with a booster 1 for generating an under pressure with respect to the pressure of the supplied biogas, in order to efficiently abduct biogas from the digester, or digesters.
  • the booster 1 Preferably the booster 1 generates a pressure of about 50 mbar.
  • Conduit 11 leads the biogas to a pre -cooler 2 wherein the biogas is cooled by using cooing water having a temperature within the range of 15°C to 20°C.
  • conduit 12 leads the cooled biogas to condenser 3, or preferably to condensate separator 3 which collects the condensed water.
  • this condensed water may be used in the present invention as cool water in pre-cooler 2 to cool the biogas, preferably via conduit 13.
  • Conduit 14 leads the biogas having reduced water content from the condenser 3 to compressor 4.
  • compressor 4 is an oil flooded rotary screw compressor.
  • Compressor 4 comprises a compressor 41, oil receiver 42, coolers 43 and a moisture separator 45.
  • Compressor 4 brings the biogas with reduced water content to a pressure of 10 bar.
  • Conduit 15 leads the pressured biogas to molecular sieves 5.
  • conduit 15 is provided with valves 6 to direct the flow of pressurized biogas to one or the other molecular sieve 5.
  • the biogas enters the molecular sieve 5 via a first inlet 51 en exits the molecular sieve 5 at first outlet 52.
  • first inlet 51 en exits the molecular sieve 5 at first outlet 52.
  • the flow of pressurized biogas is first led over the first molecular sieve part 53 having a sieving diameter of 3 A to separate remaining water from the pressurized biogas flow.
  • the biogas is led over the second sieve part 54 having a sieving diameter of 5 A to separate hydrogen sulfide from the pressurized biogas flow.
  • conduit 16 directs the produced pseudo gas, or upgraded biogas, to mixing vessel 7.
  • Mixing vessel 7 mixes the pseudo gas for a desired time period to ensure that the pseudo gas obtains an uniform composition is obtained. This produced uniform pseudo gas is abducted from the mixing vessel 7 via conduit 17.
  • conduit 16-1 or conduit 16-2 guides the pseudo gas into the second sieve part 54 via first outlet 52.
  • the flow of pseudo gas firstly separates the concentrated hydrogen sulfide from the second sieving part 54 and secondly the concentrated water from first sieving part 53.
  • the concentrated water and hydrogen sulfide having a concentration of 50.000 ppm is abducted from the molecular sieve 5 via second outlet 55 and via conduit 19 to tank 9 as shown in figure 2 and subsequently via conduit 20 to incinerator / quencher 10 in which the concentrated water and hydrogen sulfide is heated to 700° C and quenched with water.
  • the in the incinerator / quencher 10 formed sulphuric acid is abducted from the incinerator / quencher 9 via conduit 21 to acid water tank 22.
  • tank 22 the sulphuric acid is contacted with ammonia to produce ammonium sulphate.
  • the present incinerator / quencher 10 may be connected with a supply of water (not shown). Further, the acid water tank 22 may be cooled by a water circuit through the acid water tank 22 (not shown).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Gas Separation By Absorption (AREA)
  • Processing Of Solid Wastes (AREA)
  • Treating Waste Gases (AREA)

Abstract

The present invention relates to a method for upgrading biogas and production of ammonium sulphate, comprising the steps of : condensing a biogas by contacting the biogas with cooling medium to produce biogas with a reduced water content; pressurizing the biogas with a reduced water content to a pressure of about 5 to 25 bar to produce pressurized biogas; leading the pressurized biogas over a molecular sieve to separate hydrogen sulfide and to produce pseudo gas; leading the separated hydrogen sulfide to an incinerator / quencher and heating the hydrogen sulfide to a temperature above 700°C and quenching the heated hydrogen sulfide with water to produce sulphuric acid; and bringing the sulphuric acid in contact with ammonia to produce ammonium sulphate.

Description

METHOD FOR UPGRADING BIOGAS AND PRODUCTION OF AMMONIUM
SULPHATE
Description
The present invention relates according to a first aspect to a method for upgrading biogas and production of ammonium sulphate. According to another aspect the present invention relates to a system suitable for upgrading biogas and production of ammonium sulphate.
Biogas is produced by anaerobic digestion with anaerobic bacteria or by fermentation of biodegradable materials such as manure, sewage, municipal waste, green waste, plant material etc. Biogas generally comprises methane, carbon dioxide, and small amounts of hydrogen sulfide, also known as H2S. Primarily the methane can be combusted with oxygen and allows biogas to be used as a fuel. Before biogas is suitable to be used as fuel, it is commonly upgraded to concentrate the methane.
Specifically, the hydrogen sulfide which is present in biogas has a highly corrosive nature and may destroy the internals of a plant. Common upgrading methods aim to separate the hydrogen sulfide from the biogas. However, the concentrated hydrogen sulfide raises another problem because hydrogen sulfide is an undesired by product in view of its toxicity, flammability and corrosiveness. Hydrogen sulfide is difficult to store, and especially for farmers having their own digesters for biomass.
The main way to convert hydrogen sulfide is the Claus process, in which the hydrogen sulfide reacts with sulfur dioxide at high temperature and/or in presence of a catalyst. The disadvantage of the Claus process is that multi steps are required, i.e. both a thermal and a catalytic step, to convert the hydrogen sulfide to water and sulfur. Further, the disadvantage of the Claus process is that it would be difficult to perform for farmers having their own digesters for biomass.
It is an object of the present invention, amongst other objects, to provide an efficient, simple and inexpensive method for upgrading biogas and the production of ammonium sulphate from the biogas.
This objective, amongst other objectives, is met by providing a method according to the appended claim 1.
Specifically, this objective is met by providing a method for upgrading biogas and /or for the production of ammonium sulphate, comprising the steps of :
(i) condensing a biogas by contacting the biogas with a cooling medium, in a
condenser and/or pre-cooler, to produce biogas with a reduced water content; (ii) pressurizing the biogas with a reduced water content to a pressure of about 5 to 25 bar to produce pressurized biogas; (iii) leading the pressurized biogas over a molecular sieve to separate hydrogen sulfide and to produce pseudo gas;
(iv) leading the separated hydrogen sulfide to an incinerator / quencher and heating the hydrogen sulfide to a temperature above 700°C and quenching the heated hydrogen sulfide with water to produce sulphuric acid; and
(v) bringing the sulphuric acid in contact with ammonia to produce ammonium
sulphate.
The present inventors surprisingly found that the method enables the removal of hydrogen sulfide from biogas provided from a digester, wherein the amount of hydrogen sulfide in the final pseudo gas is less than 1 percent of the initial hydrogen sulfide concentration in the biogas.
Further, it was found that the sulfur component of the hydrogen sulfide advantageously could be used for the production of ammonium sulphate.
Farmers encounter several problems with ammonia because the emission of ammonia is strictly limited, and ammonia provides an undesired pungent smell. With the present method the farmer is able to convert this ammonia to ammonium sulphate, which is furthermore advantageous because ammonium sulphate is a common used fertilizer for lowering the pH of the soil while contributing essential nitrogen for plant growth.
Preferably, in the present step (i), the water content of the biogas is reduced to a water content of less than 10 % (w/w), less than 5% (w/w) or less than 1% (w/w) of the amount of water which is present before condensing. The advantage of reducing the amount of water is that the formation of sulphuric acid and/or formic acid is avoided. Both acids may be formed during processing and are very damaging for the downstream process equipment, such as a compressor.
The biogas which may be condensed in the present step (i) may be any biogas obtained from a digester. Commonly, such a biogas has a temperature of 35°C to 45°C and comprises about 75% methane and 25 carbon dioxide, as well as trace elements hydrogen sulfide. Preferably, the present biogas of step (i) is wet biogas directly obtained from digesters and/or comprises about 10,000 ppm hydrogen sulfide.
In present step (ii), the biogas with a reduced water content is pressurized to a pressure of at least 5 bar, such as 5 to 50 bar, 5 to 25 bar, preferably 6 to 15, more preferably 6 to 10 bar to produce pressurized biogas. The advantage of pressurizing the biogas with reduced water content is that a more efficient sieving of hydrogen sulfide is obtained, providing the production of pseudo gas with substantially no hydrogen sulfide.
In present step (iii) leading the pressurized biogas over a molecular sieve to separate hydrogen sulfide and to produce pseudo gas, preferably separates hydrogen sulfide with a concentration of at least 50.000 ppm. The present step (iv) of leading the separated hydrogen sulfide to an incinerator / quencher and heating the hydrogen sulfide to a temperature above 700°C and quenching the heated hydrogen sulfide with water to produce sulphuric acid preferably comprises heating the hydrogen sulfide to a temperature within the range of 700°C to 800°C.
According to a preferred embodiment, the present method comprises leading a portion of the produced pseudo gas over the molecular sieve to regenerate the molecular sieve to separate the water and/or hydrogen sulfide from the molecular sieve , while simultaneously leading the pressurized biogas over a second, or third, molecular sieve to produce pseudo gas.
Pseudo gas, or alternatively purified biogas, as used in the present context means biogas with a reduced hydrogen sulfide content, s. Leading a portion of the produced pseudo gas, such as from 1 to 15% of the produced pseudo gas, over the molecular sieve regenerates the sieve by separating the concentrated water and hydrogen sulfide from the sieve. It is advantageous to simultaneously use a second, or further, molecular sieve to continue the production of pseudo gas while the molecular sieve is regenerating since a continuous process is provided. Preferably, the present molecular sieves are regenerated by leading a portion of the produced pseudo gas first of the second part of the molecular sieve, and subsequently leading the pseudo gas over the first part of the molecular sieve.
In other words, it is preferred that the present step (iv) of leading the separated hydrogen sulfide to an incinerator / quencher and heating the hydrogen sulfide to a temperature above 700°C and quenching the heated hydrogen sulfide with water to produce sulphuric acid preferably comprises leading the separated hydrogen sulfide via a regeneration flow of produced pseudo gas over the respective molecular sieve.
According to a preferred embodiment, the present molecular sieve, or molecular sieves, is heated during the regeneration of the molecular sieve, preferably to a temperature within the range of 150°C to 500°C, more preferably 200°C to 400°C. Advantageously, the molecular sieve is heated with heat derived from the present incinerator / quencher.
According to yet another preferred embodiment, the present method comprises leading the pressurized biogas over a first part of the molecular sieve having a diameter of less than 4 A, preferably less than 3.5 A or from 2.5 A to 3.5 A, to separate water and/or comprising leading the pressurized biogas over a second part of the molecular sieve having a diameter of less than 6 A, preferably less than 5.5 A or from 4.5 A to 5.5 A, to separate hydrogen sulfide. Preferably, the present pressurized biogas is first led over the first part of the molecular sieve and subsequently led over the second part of the molecular sieve.
According to a preferred embodiment, the present method comprises mixing the pseudo gas in a mixing vessel to obtain pseudo gas having a uniform composition. The present process is a continuous process, but the composition of the produced pseudo gas fluctuates during the process. By mixing the produced pseudo gas for a time period enough to provide uniform pseudo gas, the fluctuations in the composition are minimalized. This is advantageous since the uniform pseudo gas could easier be used in combustion applications. Preferably, the present the pseudo gas or uniform pseudo gas comprises less than 100 ppm, more preferably less than 50 ppm hydrogen sulfide.
According to another preferred embodiment, the present biogas derived from a digester is brought to a pressure of 20 to 100 mbar, preferably 40 to 60 mbar, before the biogas is condensed in step (i). This pressure provides a more efficient reduction of water and thus the risk of damage of corrosive sulphuric acid or formic acid is reduced. Preferably, the biogas is supplied from a supply source, such as a digester, by using an under pressure, providing that the biogas is easily transferred to the condenser.
According to a preferred embodiment, the present cooling medium has a temperature within the range of 10°C to 25°C, preferably 15°C to 20°C. Preferably the present cooling medium is water; however another cooling medium may also be used.
According to another aspect, the present invention relates to a system suitable for upgrading biogas and/or production of ammonium sulphate, comprising, a conduit for the supply of biogas which is connected to a cooler and/or a condenser, the condenser is further connected via a conduit to a compressor suitable to pressurize a gas stream to 5 to 25 bar, which compressor is connected via a conduit to a first inlet of a molecular sieve, which molecular sieve is preferably connected via a first outlet and conduit with a mixing vessel, and preferably with a second outlet with an incinerator / quencher, which incinerator / quencher is connected via a conduit with an acid water tank.
The system according to the present invention is a compact system that conveniently can be connected with digesters. In this way, the present system provides upgrading of the biogas from the digester, while simultaneously hydrogen sulfide separated from the biogas is used for the production of ammonium sulphate. Accordingly, the present invention provides an easy and efficient onsite system for the production of both ammonium sulphate and pseudo gas, or purified biogas.
According to a preferred embodiment, the present compressor is connected with a further first inlet of a second molecular sieve, which second molecular sieve is connected via a first outlet and conduit with the mixing vessel. Accordingly, the first and second molecular sieves are situated in parallel between the compressor and the mixing vessel. This provides the advantage that the second molecular sieve can be used for separating water and/or hydrogen sulfide from the pressurized biogas while the first molecular sieve will be regenerated, and vice versa.
According to yet another preferred embodiment, on the conduit between the first outlet and the mixing vessel is connected another conduit connecting to the mixing vessel, enabling backflow of pseudo gas from the mixing vessel to the first outlet of the molecular sieve. This backflow of pseudo gas from the mixing vessel towards the first or second molecular sieve provides regeneration of the respective molecular sieve by separating the concentrated water and/or hydrogen sulfide from the molecular sieve. Furthermore, this backflow leads the concentrated hydrogen sulfide towards the present incinerator / quencher.
According to a preferred embodiment, the present molecular sieve comprises a first part having a sieve diameter of less than 4 A, preferably less than 3.5 A or from 2.5 A to 3.5 A, to separate water and/or comprising leading the pressurized biogas over a second part of the molecular sieve having a diameter of less than 6 A, preferably less than 5.5 A or from 4.5 A to 5.5 A to separate hydrogen sulfide. Preferably, the second part is connected to the first outlet of the molecular sieve.
According to a preferred embodiment, the present molecular sieve is provided with heating means configured to heat the sieve to a temperature within the range of 150°C to 500°C.
Preferably, the heating means derive heat from the present incinerator / quencher.
According to another preferred embodiment, the present conduit for the supply of biogas is provided with a compressor configured to bring the biogas to a pressure of 20 to 100 mbar.
The present invention will be further elucidated with reference to figures 1 and 2 showing a preferred system according to the present invention.
Specifically, figure 1 shows a conduit 11 for the supply of biogas from a digester. Conduit 11 is preferably provided with suitable valves to regulate the flow of biogas. Further, conduit 11 is provided with a booster 1 for generating an under pressure with respect to the pressure of the supplied biogas, in order to efficiently abduct biogas from the digester, or digesters. Preferably the booster 1 generates a pressure of about 50 mbar. Conduit 11 leads the biogas to a pre -cooler 2 wherein the biogas is cooled by using cooing water having a temperature within the range of 15°C to 20°C. Subsequently conduit 12 leads the cooled biogas to condenser 3, or preferably to condensate separator 3 which collects the condensed water. Preferably this condensed water may be used in the present invention as cool water in pre-cooler 2 to cool the biogas, preferably via conduit 13. Conduit 14 leads the biogas having reduced water content from the condenser 3 to compressor 4. In this example, compressor 4 is an oil flooded rotary screw compressor. However other compressor type may also be used in the present context. Compressor 4 comprises a compressor 41, oil receiver 42, coolers 43 and a moisture separator 45. Compressor 4 brings the biogas with reduced water content to a pressure of 10 bar. Conduit 15 leads the pressured biogas to molecular sieves 5. Specifically, conduit 15 is provided with valves 6 to direct the flow of pressurized biogas to one or the other molecular sieve 5. The biogas enters the molecular sieve 5 via a first inlet 51 en exits the molecular sieve 5 at first outlet 52. Thus, the flow of pressurized biogas is first led over the first molecular sieve part 53 having a sieving diameter of 3 A to separate remaining water from the pressurized biogas flow. Subsequently, the biogas is led over the second sieve part 54 having a sieving diameter of 5 A to separate hydrogen sulfide from the pressurized biogas flow. As shown in figure 1, conduit 16 directs the produced pseudo gas, or upgraded biogas, to mixing vessel 7. Mixing vessel 7 mixes the pseudo gas for a desired time period to ensure that the pseudo gas obtains an uniform composition is obtained. This produced uniform pseudo gas is abducted from the mixing vessel 7 via conduit 17. About 10% of the uniform pseudo gas abducted from the mixing vessel 7 is directed via conduit 17 to conduit 15-1 or conduit 15-2 via valves 8. Subsequently, conduit 16-1 or conduit 16-2 guides the pseudo gas into the second sieve part 54 via first outlet 52. The flow of pseudo gas firstly separates the concentrated hydrogen sulfide from the second sieving part 54 and secondly the concentrated water from first sieving part 53. Thereafter the concentrated water and hydrogen sulfide having a concentration of 50.000 ppm is abducted from the molecular sieve 5 via second outlet 55 and via conduit 19 to tank 9 as shown in figure 2 and subsequently via conduit 20 to incinerator / quencher 10 in which the concentrated water and hydrogen sulfide is heated to 700° C and quenched with water. Subsequently as shown in figure 2, the in the incinerator / quencher 10 formed sulphuric acid is abducted from the incinerator / quencher 9 via conduit 21 to acid water tank 22. In tank 22 the sulphuric acid is contacted with ammonia to produce ammonium sulphate. In order to quench the incinerated hydrogen sulfide the present incinerator / quencher 10 may be connected with a supply of water (not shown). Further, the acid water tank 22 may be cooled by a water circuit through the acid water tank 22 (not shown).

Claims

1. Method for upgrading biogas and production of ammonium sulphate, comprising the steps of :
(i) condensing a biogas by contacting the biogas with cooling medium to produce biogas with a reduced water content;
(ii) pressurizing the biogas with a reduced water content to a pressure of about 5 to 25 bar to produce pressurized biogas;
(iii) leading the pressurized biogas over a molecular sieve to separate hydrogen sulfide and to produce pseudo gas;
(iv) leading the separated hydrogen sulfide to an incinerator / quencher and heating the hydrogen sulfide to a temperature above 700°C and quenching the heated hydrogen sulfide with water to produce sulphuric acid; and
(v) bringing the sulphuric acid in contact with ammonia to produce ammonium
sulphate.
2. Method according to claim 1 , comprising leading a portion of the produced pseudo gas over the molecular sieve to regenerate the molecular sieve, while simultaneously leading the pressurized biogas over a second molecular sieve to produce pseudo gas.
3. Method according to clause 1 or claim 2, comprising leading the pressurized biogas over a first part of the molecular sieve having a diameter of less than 4 A to separate water and/or comprising leading the pressurized biogas over a second part of the molecular sieve having a diameter of less than 6 A to separate hydrogen sulfide.
4. Method according to any of the claims 1 to 3, wherein the molecular sieve is heated during the regeneration of the molecular sieve, preferably to a temperature within the range of 150°C to 500°C, more preferably 150°C to 400°C.
5. Method according to any of the claims 1 to 4, wherein the biogas of step (i) is wet biogas directly obtained from digesters, comprising about 10,000 ppm hydrogen sulfide.
6. Method according to any of the claims 1 to 5, further comprising mixing the pseudo gas in a mixing vessel to obtain pseudo gas having a uniform composition.
7. Method according to any of the claims 1 to 6, wherein the pseudo gas comprises less than 100 ppm hydrogen sulfide.
8. Method according to any of the claims 2 to 7, wherein the biogas is brought to a pressure of 20 to 100 mbar, preferably 40 to 60 mbar, before the biogas is condensed in step (i).
9. Method according to any of the claims 1 to 8, wherein the cooling water has a temperature within the range of 10°C to 25°C, preferably 15°C to 20°C.
10. System suitable for upgrading biogas and production of ammonium sulphate, comprising, a conduit for the supply of biogas which is connected to a cooler and a condenser, the condenser is further connected via a conduit to a compressor suitable to pressurize a gas stream to 5 to 25 bar, which compressor is connected via a conduit to a first inlet of a molecular sieve, which molecular sieve is connected via a first outlet and conduit with a mixing vessel and with a second outlet with an incinerator / quencher, which incinerator / quencher is connected via a conduit with an acid water tank.
11. System according to claim 10, wherein the compressor is connected with a further first inlet of a second molecular sieve, which second molecular sieve is connected via a first outlet and conduit with the mixing vessel.
12. System according to claim 10 or 11, wherein on the conduit between the first outlet and the mixing vessel is connected another conduit connecting to the mixing vessel, enabling backflow of pseudo gas from the mixing vessel to the first outlet of the molecular sieve.
13. System according to any of the claims 10 to 12, wherein the molecular sieve comprises a first part having a sieve diameter of less than 4 A to separate water and a second part of the molecular sieve having a diameter of less than 6 A to separate hydrogen sulfide.
14. System according to any of the claims 10 to 13, wherein the molecular sieve is provided with heating means configured to heat the sieve to a temperature within the range of 150°C to 500°C.
15. System according to any of the claims 10 to 14, wherein the conduit for the supply of biogas is provided with a compressor configured to bring the biogas to a pressure of 20 to 100 mbar.
EP15736839.0A 2014-07-21 2015-07-14 Method for upgrading biogas and production of ammonium sulphate Withdrawn EP3177383A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL2013230A NL2013230B1 (en) 2014-07-21 2014-07-21 Method for upgrading biogas and production of ammonium sulphate.
PCT/EP2015/066074 WO2016012309A1 (en) 2014-07-21 2015-07-14 Method for upgrading biogas and production of ammonium sulphate

Publications (1)

Publication Number Publication Date
EP3177383A1 true EP3177383A1 (en) 2017-06-14

Family

ID=51493009

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15736839.0A Withdrawn EP3177383A1 (en) 2014-07-21 2015-07-14 Method for upgrading biogas and production of ammonium sulphate

Country Status (5)

Country Link
EP (1) EP3177383A1 (en)
AR (1) AR102805A1 (en)
NL (1) NL2013230B1 (en)
TW (1) TW201604134A (en)
WO (1) WO2016012309A1 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10239016B2 (en) 2016-12-07 2019-03-26 Nuorganics LLC Systems and methods for nitrogen recovery from a gas stream
MX2020011624A (en) 2017-01-16 2020-12-07 Nuorganics LLC System and method for recovering nitrogenous compounds from a gas stream.
CN108624370B (en) * 2017-03-20 2021-04-06 中国石油化工股份有限公司 Method for preparing biological methane by separating and purifying methane membrane
CN108816000B (en) * 2018-06-14 2020-10-16 杭州兴洋环保科技有限公司 Resourceful treatment method for purifying air polluted by hydrogen sulfide and ammonia gas by using plasma
CN108816003A (en) * 2018-08-06 2018-11-16 临安姚希自动化科技有限公司 Intelligence blots machine control system
WO2022220681A1 (en) 2021-04-16 2022-10-20 Gashouders B.V. Compression of a biogas containing carbon dioxide, compressed biogas containing carbon dioxide, and use thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NZ553992A (en) * 2007-03-20 2008-10-31 Flotech Holdings Ltd Biogas treatments for increasing the methane concentration
US20110185896A1 (en) * 2010-02-02 2011-08-04 Rustam Sethna Gas purification processes
US20120264197A1 (en) * 2011-04-15 2012-10-18 Guild Associates, Inc. H2S Removal from Contaminated Gases
CA2737825A1 (en) * 2011-04-20 2012-10-20 Carbon Solutions Incorporated Conversion of acid gas to sulphate or phosphate-based fertilizers
US8859831B2 (en) * 2011-08-02 2014-10-14 Gas Technology Institute Removal of hydrogen sulfide as ammonium sulfate from hydropyrolysis product vapors
EP2790810A1 (en) * 2011-12-16 2014-10-22 DGE Dr.-Ing. Günther Engineering GmbH Process and plant for removal of carbon dioxide from methane-containing crude gases
KR101442730B1 (en) * 2012-12-31 2014-09-23 디에이치엠(주) Apparatus for preprocessing of bio-gas

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
None *
See also references of WO2016012309A1 *

Also Published As

Publication number Publication date
AR102805A1 (en) 2017-03-29
TW201604134A (en) 2016-02-01
NL2013230B1 (en) 2016-08-16
WO2016012309A1 (en) 2016-01-28

Similar Documents

Publication Publication Date Title
WO2016012309A1 (en) Method for upgrading biogas and production of ammonium sulphate
US7811455B2 (en) Removal of ammonia from fermentation effluent and sequestration as ammonium bicarbonate and/or carbonate
US8500864B2 (en) Method and plant for treating crude gas, in particular biogas, containing methane and carbon dioxide in order to produce methane
RU2571146C2 (en) Separation method
CN105518147B (en) Apparatus for producing organic substance and method for producing organic substance
JP6683843B2 (en) Phosphate recovery method
RU2653841C2 (en) Removal of hydrogen sulphide as ammonium sulphate from hydropyrolysis product vapours
WO2005056723A1 (en) Method and system for the torrefaction of raw materials
US10421674B2 (en) Process and plant for separating off and/or recovering nitrogen compounds from a liquid or sludge substrate
CN104843813A (en) Coal gasification high ammonia nitrogen wastewater treatment process
JP2016131549A (en) Method and apparatus for synthesizing ethanol
WO2020160998A1 (en) A process for cleaning biogas while producing a sulfur-containing fertilizer
JP5797150B2 (en) Magnesium ammonium phosphate production suppression system and methane fermentation system
CN104628012A (en) Production method for preparing ammonium sulfate by alkylating waste acid
US8828124B1 (en) Biogas purification apparatus and method for operation thereof
US11634349B2 (en) Two-stage biogas production system for anaerobic digesters
US20230278880A1 (en) Ammonium Bicarbonate Production Method Using Anaerobic Digester Outputs
JP2012125701A (en) Ammonia removing device, and apparatus and method for treating organic waste using the same
US11999664B2 (en) Processes and systems for producing ammonia products and/or calcium carbonate products
CN112499647A (en) Hydrogen recovery process
US20210269371A1 (en) Aqueous and solid ammonium sulfate fertilizers and methods of producing
WO2017186357A1 (en) Process and plant for the purification of process condensate from the catalytic steam reformation of a hydrocarbonaceous feed gas
US20230026882A1 (en) Methods of producing ammonium bicarbonate during the production of organic fertilizers
NL2003086C2 (en) METHOD AND DEVICE FOR HANDLING AMMONIUM WASTE WATER.
EP3517618B1 (en) Method and apparatus for producing valuable substance

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20170216

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20171213

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20190201