WO2011072877A1 - Process for the production of hydrogen starting from liquid hydrocarbons, gaseous hydrocarbons and/or oxygenated compounds also deriving from biomasses - Google Patents
Process for the production of hydrogen starting from liquid hydrocarbons, gaseous hydrocarbons and/or oxygenated compounds also deriving from biomasses Download PDFInfo
- Publication number
- WO2011072877A1 WO2011072877A1 PCT/EP2010/007772 EP2010007772W WO2011072877A1 WO 2011072877 A1 WO2011072877 A1 WO 2011072877A1 EP 2010007772 W EP2010007772 W EP 2010007772W WO 2011072877 A1 WO2011072877 A1 WO 2011072877A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- section
- process according
- ranging
- gas
- produced
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/386—Catalytic partial combustion
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
- C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
- C01B2203/0288—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step containing two CO-shift steps
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0415—Purification by absorption in liquids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/042—Purification by adsorption on solids
- C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0495—Composition of the impurity the impurity being water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0872—Methods of cooling
- C01B2203/0883—Methods of cooling by indirect heat exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1247—Higher hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1258—Pre-treatment of the feed
- C01B2203/1264—Catalytic pre-treatment of the feed
- C01B2203/127—Catalytic desulfurisation
Definitions
- the present invention relates to a process for the production of hydrogen starting from liquid hydrocarbons, gaseous hydrocarbons, and/or oxygenated compounds, also deriving from biomasses, and mixtures thereof. Said process comprises:
- Said process can possibly comprise a hydro- desulphuration section of said feedstock.
- SR Steam Reforming
- the combustion serves to provide heat to the reactions which are extremely endothermic .
- the hydrocarbons enter the reforming tubes after being mixed with significant quantities of steam (the [steam moles/carbon moles] ratio is typically higher than 2.5) and are transformed into a mixture prevalently containing H 2 and CO (synthesis gas) .
- the catalysts used typically contain Nickel deposited on an oxide carrier.
- the inlet temperatures into the tubes are typically higher than 600 °C, whereas the temperatures of the gases leaving the tubes are lower than 900°C.
- the pressure at which the SR process takes place typically ranges from 5 relative bar to 30 relative bar .
- the SR process takes place in a tubular reactor in which the tubes are inserted in a radiant chamber and in which the reaction heat is supplied through wall or vault burners.
- the reaction tubes have a diameter ranging from 3" to 5" and a length of 6 metres to 13 metres; said tubes are filled with catalyst and the mixture composed of hydrocarbons and steam passes through them.
- the wall temperature of said tubes is about [100- 150] °C higher and that of the fumes generated by the burners is [1200-1300] °C.
- These tubes constructed by fusion with special alloys having a high Cr and Ni content ( [25 - 35]%) , consequently represent a critical element of the technology.
- the necessity of avoiding impingement between the tubes and flames of the burners, which would lead to the instantaneous collapse of the tubes, requires their distancing and consequently an increase in the volume of the reforming oven.
- a further critical aspect of the SR process relates to the impossibility of using high-molecular- weight hydrocarbons, which can lead to the formation of carbonaceous residues with a reduction in the catalytic activity.
- the heat supplied to the outside of the tubes causes cracking phenomena of the hydrocarbons, with a further formation of carbonaceous residues, of which the most extreme consequence is the blockage of the reforming tubes and their breakage .
- the sulphurated compounds if fed to the SR process, can also cause deactivation of the catalyst and create analogous consequences. For this reason, for the SR process, the feedstock must be hydro-desulphurated before being used.
- SCT-CPO short contact time - catalytic partial oxidation
- MI93A001857, MI96A000690, MI 2002AO 01133 , MI2007A002209 and MI 2007A002228 of L. Basini et al the hydrocarbons mixed with air and/or oxygen are passed over a suitable catalyst and transformed into synthesis gas.
- the reaction heat is generated inside the reactor, by balancing the total and partial oxidation reactions of the feedstock.
- the main reaction of the SCT-CPO process is represented by the equation [2] :
- the volume of catalyst required amounts to about 21 Tons. It is also specified that the reaction section and thermal recovery section from the fumes of the reforming oven have considerable dimensions and occupy a volume of approximately 11,000 m 3 .
- the same quantity of H 2 could, on the other hand, be produced by an SCT-CPO reactor and a thermal recovery section having a total volume of about 70 m 3 and containing 0.85 Tons of catalyst.
- the synthesis gas leaving the reforming oven is shifted to a mixture of H 2 and C0 2 by reacting the CO with water vapour in one or more Water Gas Shift (WGS) reactors according to the reaction [3] :
- the H 2 is subsequently separated and purified typically using a Pressure Swing Adsorption (PSA) section.
- PSA Pressure Swing Adsorption
- the PSA section therefore releases a stream of pure H 2 and a stream of low-pressure purge gas which mainly comprises C0 2 , CH 4 and a part of the H 2 produced.
- Said purge gas which has a heat power (PCI) typically within the range of [2,000-2,500] kcal/kg, it is then fed again to the reformer oven supplying a part of the reaction heat.
- PCI heat power
- One of the disadvantages of the SR reaction is the export production of steam, i.e. an excess production of steam which cannot be recovered in the process and whose presence reduces the energy efficiency of the process itself .
- a similar process scheme can also be used in the SCT-CPO technology destined for the production of H 2 .
- the partial pressure of the C0 2 produced at the outlet of the WGS section is higher than that obtained in the SR process, and consequently not only the flow-rate of the gas to be purified is higher in PSA, but also the purge gas leaving the PSA has a lower heat power with respect to that obtained by means of SR.
- a purge gas with an excessively low heat power value cannot easily be used for the production of steam in a boiler.
- An objective of the present invention is to provide a new process architecture which combines a SCT-CPO section, a WGS section and a C0 2 removal section in order to obtain a stream of H 2 , with purity higher than 90% v/v, separated from a stream of pure C0 2 .
- a PSA section situated after the C0 2 removal section. This PSA unit allows high-purity H 2 and a purge gas with a medium heat power, to be obtained.
- a further objective of the present invention is therefore to produce streams of high-purity H 2 and C0 2 and a purge gas leaving the PSA with a medium-high heat power (PCI) , which is such as to allow it to be used directly in combustion processes and/or introduced into the fuel supply system of a plant.
- PCI medium-high heat power
- a further objective of the present invention is to allow the production of synthesis gas containing lower quantities of sulphurated compounds, which could be eliminated in the C0 2 removal step and/or in the possible PSA step.
- the present invention relates to a process for the production of hydrogen starting from reagents comprising liquid hydrocarbons, gaseous hydrocarbons, and/or oxygenated compounds, also deriving from biomasses, and mixtures thereof, wherein the gaseous hydrocarbons are selected from the group comprising natural gas, liquefied petroleum gas, gaseous hydrocarbon streams coming from operative processes in refineries and/or any chemical plant and mixtures thereof, wherein the liquid hydrocarbons are selected from the group comprising naphthas, gas oils, high- boiling gas oils, light cycle oils, heavy cycle oils, deasphalted oils, and mixtures thereof, and wherein the oxygenated compounds are selected from the group comprising glycerine, triglycerides, carbohydrates, methanol, ethanol, and mixtures thereof, said process characterized in that it comprises:
- a heat recovery section including a boiler which generates steam thus cooling the synthesis gas produced
- a further embodiment of the present invention relates to a process as previously described possibly comprising a purification section of the hydrogen produced by means of Pressure Swing Adsorption and the generation of purge gas having a medium heat power.
- the purge gas can possibly be used in a combustion process and/or be introduced into the fuel supply system of a refinery or any other chemical plant. Having considerably reduced the flow-rate to the PSA, thanks to the removal of the C0 2 , the possible final purification of the hydrogen is more efficient and less costly. Furthermore, this process greatly reduces emissions such as NOx, CO and particulates, as the preheating of the feedstocks can preferably be effected with the steam produced by the cooling of the synthesis gas leaving the SCT-CPO reactor. Process schemes which adopt the synthesis gas production technology via SCT- CPO may also not use preheating ovens of the reagents; it is therefore always possible to avoid producing diluted streams of C0 2 in the combustion fumes .
- the process configuration can be such as to not cause the production of an excess of steam.
- the export of steam in fact, is not always advantageous and in some cases it may be advisable to avoid it.
- a further embodiment of the present invention relates to a process as previously described which possibly comprises a hydrodesulphuration section of the reagents .
- the process integration between the hydrodesulphuration section, SCT-CPO, WGS reaction, C0 2 removal and PSA can also be formulated so as to not cause any emission of C0 2 in diluted streams different from that obtained from the removal unit.
- the SR technology does not allow a process scheme to be formulated in which an overproduction of steam (we repeat that the export of steam in fact is not always advantageous or necessary in all industrial contexts) or the emission of C0 2 in the fumes of the preheating and SR ovens, can be avoided.
- the quantity of C0 2 emitted and "not recoverable" corresponds to percentages ranging from 30% v/v to 45% v/v of the total quantity of C0 2 produced.
- FIG. 1 shows a block scheme of the production process of hydrogen in which:
- ⁇ 100 is the hydrodesulphuration section
- BFW Boiling Feed Water
- ⁇ 300 is the purge gas compression.
- FIG. 2 shows a block scheme of the production process of hydrogen similar to Figure 1 except for the block P (WGS) which in this figure comprises:
- HTS high-temperature shift
- 207 is a Boiling Feed Water (BFW) cooler.
- the feeding (2) is possibly hydro-desulphurated, it is subsequently mixed with the oxidant (1) and preheated before reacting in a catalytic partial oxidation section (101) in which the reagents are converted into synthesis gas (4) .
- the hot synthesis gas is cooled by means of a heat recovery boiler (201) and the high- temperature steam (5) thus produced is possibly used partly for the preheating phase of the reagents (200) , and partly for sustaining the Water Gas Shift reaction (102) .
- the cooled synthesis gas (19) is converted in the WGS section (102) into the mixture comprising hydrogen and carbon dioxide (9) .
- Said mixture is cooled by means of a Boiling Feed Water cooler (202) and a water exchanger (204) thus producing low-pressure steam (13 and 20) .
- the cooling is completed with an air exchanger (203) .
- a separator (103) removes the condensate and the mixture thus obtained enters a C0 2 removal section (104) . If this section functions with an amine solution, part of the low- pressure steam produced (13 and 20) can possibly be used for washing said solution.
- a stream of H 2 (15) and a stream of C0 2 (14) leave 104.
- the hydrogen enters a possible purification section (105) from which pure hydrogen (16) exits together with purge gas (21) , which can be used partly as fuel in the possible preheating oven of the reagents (3) and can be partly compressed for other purposes (300) .
- the process, object of the present invention comprises the phases described hereunder .
- the feeding (2) comprises liquid hydrocarbons, gaseous hydrocarbons, and/or oxygenated compounds, also deriving from biomasses, and mixtures thereof.
- the gaseous hydrocarbons comprise natural gas, liquefied petroleum gas, gaseous hydrocarbon streams coming from operative processes in refineries and/or any chemical plant and mixtures thereof.
- the liquid hydrocarbons comprise naphthas, gas oils, high-boiling gas oils, light cycle oils, heavy cycle oils, deasphalted oils, and mixtures thereof.
- the oxygenated compounds comprise glycerine, triglycerides, carbohydrates, methanol, ethanol and mixtures thereof .
- the feeding (2) possibly enters the hydrodesulfphuration section (100) where the sulphur is initially converted to sulphidric acid and is subsequently reacted with zinc oxide so that the outgoing feedstock contains less than 0.1 ppm of sulphur.
- the hydrodesulfphuration section may not be the initial step of the process as the catalytic partial oxidation section (101) is capable of also operating with sulphurated feedstocks.
- the hydrodesulfphuration section (100) can be situated downstream of a Water Gas Shift Sulphur Tolerant section (not indicated in Figure 1) .
- the stream leaving the hydrodesulfphuration section is mixed with the oxidant (1) , selected from oxygen, air and air enriched in oxygen.
- Said mixture is preheated (200) to a temperature ranging from 100°C to 500°C before entering the short contact time - catalytic partial oxidation section (101) .
- the preheating can possibly take place in an oven exploiting a part of the purge gas generated (3) .
- the preheating (200) preferably exploits a part of the steam produced in the process itself (5) .
- the hydrocarbon compounds and/or oxygenated compounds react with the oxidant to give synthesis gas (4), i.e. a mixture of hydrogen and carbon monoxide.
- synthesis gas (4) i.e. a mixture of hydrogen and carbon monoxide.
- the preferred operative conditions in a short contact time - catalytic partial oxidation reactor are:
- GHSV is defined as an hourly volumetric flow of gaseous reagents divided by the volume of catalyst
- outlet temperature from the reactor ranging from 500 to 1,100 °C, preferably from 650°C to 1,050°C and more preferably ranging from 750°C to 1,000°C.
- the catalytic partial oxidation reaction is exothermic, it is therefore preferable to recover the heat transported by the synthesis gas through a boiler in which water (6) enters (possibly generated in the process) and from which high-temperature steam exits (H.T. Steam or 5) .
- H.T. Steam high-temperature steam exits
- the mixture of H 2 and C0 2 is cooled with water by means of a Boiling Feed Water cooler (202) and is then cooled with an air exchanger (203) and with a water exchanger (204) before being sent to a section which removes the condensate (103) .
- the gas (9) is sent to the carbon dioxide removal section (104) .
- the C0 2 removal section preferably includes an amine washing section, but it can also include any other system. This section preferably removes at least 98% of the carbon dioxide contained in the synthesis gas.
- the gaseous stream obtained contains a high percentage of H 2 , preferably higher than 80% v/v, but even more preferably higher than 90% v/v, said stream can be treated by a PSA section having reduced dimensions (105) .
- Said PSA section allows a high recovery factor of the H 2 produced (16) to be obtained, higher than 85% v/v and preferably higher than 90% v/v.
- the total or almost total lack of C0 2 in the stream which can be sent to the PSA significantly increases the heat power of the purge stream allowing it to be re-used in combustion processes and/or to be introduced into the fuel supply system of a refinery or any other chemical plant.
- part of the purge gas (3) is used as fuel for a preheating oven of the reagents (200) , before entering the SCT-CPO section.
- the purge gas separated by means of PSA in fact, has a relatively high heat power, with a value at least equal to 4,000 kcal/kg, preferably ranging from 4,500 kcal/kg to 7,000 kcal/kg and even more preferably ranging from 5,000 kcal/kg to 6,000 kcal/kg.
- Table 1 compares the consumptions of two typical
- Example 1 refers to Figure 2.
- Table 1 The specific consumptions indicated in Table 1 were evaluated using, for Steam Reforming, the data indicated by the licensees, whereas for the SCT-CPO technology have been reported the consolidated data at a bench and pilot scale level.
- Information relating to widely-diffused technologies was also used for the other units in the hydrodesulfphuration ( 100 ) , WGS ( 106 , 205 , 206 , 207 and 107 ) , PSA ( 105 ) and C0 2 removal ( 104 ) sections.
- the electric consumptions for the compression operations and separation of the oxygen in the Air Separation Unit have not been inserted.
- the SCT-CPO technology is jeopardized by a higher consumption of cooling water and electric consumption relating to the cryogenic unit for separating the air and obtaining pure oxygen. Between the two, the cost of electric energy is almost two orders of magnitude higher.
- the advantage of the SCT-CPO technology is consequently greater in countries in which the energy cost is lower. It should be noted that the advantage with respect to consumptions is additional to that relating to the investment costs, as the complexity of the synthesis gas production section is considerably reduced passing from the SR technology to the SCT-CPO technology.
- Example 1 the process configuration adopted for the SCT-CPO process is clearly more advantageous in contexts in which the "sequestration" and re-use of C0 2 is rewarding and in contexts in which the cost of electric energy is low.
- the percentage reduction in the investment costs relating to the reduction in the complexity of the synthesis gas production section of the SCT-CPO process increases with respect to the SR process .
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10792851A EP2512980A1 (en) | 2009-12-16 | 2010-12-15 | Process for the production of hydrogen starting from liquid hydrocarbons, gaseous hydrocarbons and/or oxygenated compounds also deriving from biomasses |
US13/516,482 US20120301391A1 (en) | 2009-12-16 | 2010-12-15 | Process for the production of hydrogen starting from liquid hydrocarbons, gaseous hydrocarbons and/or oxygenated compounds also deriving from biomasses |
CA2783744A CA2783744A1 (en) | 2009-12-16 | 2010-12-15 | Process for the production of hydrogen starting from liquid hydrocarbons, gaseous hydrocarbons and/or oxygenated compounds also deriving from biomasses |
RU2012126748/05A RU2556671C2 (en) | 2009-12-16 | 2010-12-15 | Method of obtaining hydrogen based on liquid hydrocarbons, gaseous hydrocarbons and/or oxygen-containing compounds, including those obtained from biomass |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ITMI2009A002199 | 2009-12-16 | ||
ITMI2009A002199A IT1398292B1 (en) | 2009-12-16 | 2009-12-16 | PROCESS FOR THE PRODUCTION OF HYDROGEN FROM LIQUID HYDROCARBONS, GASEOUS HYDROCARBONS AND / OR OXYGENATED COMPOUNDS ALSO DERIVING FROM BIOMASS |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011072877A1 true WO2011072877A1 (en) | 2011-06-23 |
Family
ID=42289557
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2010/007772 WO2011072877A1 (en) | 2009-12-16 | 2010-12-15 | Process for the production of hydrogen starting from liquid hydrocarbons, gaseous hydrocarbons and/or oxygenated compounds also deriving from biomasses |
Country Status (6)
Country | Link |
---|---|
US (1) | US20120301391A1 (en) |
EP (1) | EP2512980A1 (en) |
CA (1) | CA2783744A1 (en) |
IT (1) | IT1398292B1 (en) |
RU (1) | RU2556671C2 (en) |
WO (1) | WO2011072877A1 (en) |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013062415A1 (en) * | 2011-10-26 | 2013-05-02 | Stamicarbon B.V. Acting Under The Name Of Mt Innovation Center | Method for producing synthesis gas for methanol production |
WO2016016257A1 (en) | 2014-07-29 | 2016-02-04 | Eni S.P.A. | Integrated sct-cpo/pox process for producing synthesis gas |
WO2016016253A1 (en) * | 2014-07-29 | 2016-02-04 | Eni S.P.A. | Integrated short contact time catalytic partial oxidation/gas heated reforming process for the production of synthesis gas |
WO2016016256A1 (en) * | 2014-07-29 | 2016-02-04 | Eni S.P.A. | Integrated sct-cpo/atr process for the production of synthesis gas |
WO2016016251A1 (en) | 2014-07-29 | 2016-02-04 | Eni S.P.A. | Integrated sct-cpo/sr process for producing synthesis gas |
US9932229B2 (en) | 2011-07-26 | 2018-04-03 | Stamicarbon B.V. | Method and system for production of hydrogen rich gas mixtures |
EP2794465B1 (en) | 2011-12-19 | 2018-07-18 | Stamicarbon B.V. acting under the name of MT Innovation Center | Process for producing ammonia and urea |
US10435343B2 (en) | 2016-04-13 | 2019-10-08 | Northwestern University | Efficient catalytic greenhouse gas-free hydrogen and aldehyde formation from alcohols |
LU102057B1 (en) | 2020-09-09 | 2022-03-09 | Wurth Paul Sa | Method for operating a blast furnace installation |
EP3844135B1 (en) | 2018-08-29 | 2022-08-24 | ENI S.p.A. | Method and system for synthesizing methanol |
IT202100011189A1 (en) | 2021-05-03 | 2022-11-03 | Nextchem S P A | LOW ENVIRONMENTAL IMPACT PROCESS FOR THE REDUCTION OF IRON MINERALS IN A BLAST FURNACE USING SYNTHETIC GAS |
IT202100012551A1 (en) | 2021-05-14 | 2022-11-14 | Rosetti Marino S P A | CO2 CONVERSION PROCESS |
IT202100015473A1 (en) | 2021-06-14 | 2022-12-14 | Nextchem S P A | METHOD OF PRODUCTION OF CATALYST FOR HIGH TEMPERATURE CHEMICAL PROCESSES AND THE CATALYST OBTAINED THUS |
LU500764B1 (en) | 2021-10-19 | 2023-04-20 | Wurth Paul Sa | Method for reducing carbon footprint in operating a metallurgical plant for producing pig iron |
WO2024165142A1 (en) | 2023-02-07 | 2024-08-15 | NextChem S.p.A. | Process of direct reduction of iron ores by means of synthesis gas produced with catalytic partial oxidation |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2013282904B2 (en) | 2012-06-27 | 2016-11-03 | Grannus, Llc | Polygeneration production of power and fertilizer through emissions capture |
EP3150553A1 (en) * | 2015-09-30 | 2017-04-05 | Casale SA | Method for purification of a co2 stream |
MX2018006784A (en) | 2015-12-04 | 2018-11-09 | Grannus Llc | Polygeneration production of hydrogen for use in various industrial processes. |
EP3538746A1 (en) | 2016-11-09 | 2019-09-18 | 8 Rivers Capital, LLC | Systems and methods for power production with integrated production of hydrogen |
AU2018364702B2 (en) * | 2017-11-09 | 2024-01-11 | 8 Rivers Capital, Llc | Systems and methods for production and separation of hydrogen and carbon dioxide |
KR20220020842A (en) | 2019-06-13 | 2022-02-21 | 8 리버스 캐피탈, 엘엘씨 | Power production with co-generation of additional products |
US11691874B2 (en) | 2021-11-18 | 2023-07-04 | 8 Rivers Capital, Llc | Apparatuses and methods for hydrogen production |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1158617A (en) * | 1956-09-21 | 1958-06-17 | Azote & Prod Chim | Process for the preparation of gases rich in hydrogen by controlled catalytic oxidation of hydrocarbons |
US20040178124A1 (en) * | 2003-03-11 | 2004-09-16 | Ke Liu | Hydrogen desulfurizer for hydrocarbon feeds with separated adsorption and catalyst material |
US20050268554A1 (en) * | 2004-06-07 | 2005-12-08 | Ke Liu | Compact production of reformate and segregated H2, N2 and CO2 |
US20070122339A1 (en) * | 2005-11-28 | 2007-05-31 | General Electric Company | Methods and apparatus for hydrogen production |
US20070130831A1 (en) * | 2005-12-08 | 2007-06-14 | General Electric Company | System and method for co-production of hydrogen and electrical energy |
EP2072459A1 (en) * | 2007-11-21 | 2009-06-24 | ENI S.p.A. | Enhanced process for the production of synthesis gas starting from oxygenated compounds deriving from biomasses |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4476683A (en) * | 1982-12-20 | 1984-10-16 | General Electric Company | Energy efficient multi-stage water gas shift reaction |
NZ264173A (en) * | 1993-08-24 | 1995-09-26 | Shell Int Research | Catalytic process for the partial oxidation of hydrocarbons |
ITMI20031739A1 (en) * | 2003-09-11 | 2005-03-12 | Enitecnologie Spa | CATALYTIC PARTIAL OXIDATION PROCEDURE FOR |
MXPA06013098A (en) * | 2004-05-28 | 2007-04-27 | Hyradix Inc | Hydrogen generation process using partial oxidation/steam reforming. |
US7261751B2 (en) * | 2004-08-06 | 2007-08-28 | Conocophillips Company | Synthesis gas process comprising partial oxidation using controlled and optimized temperature profile |
GB0501254D0 (en) * | 2005-01-21 | 2005-03-02 | Bp Chem Int Ltd | Process |
WO2006097703A1 (en) * | 2005-03-14 | 2006-09-21 | Geoffrey Gerald Weedon | A process for the production of hydrogen with co-production and capture of carbon dioxide |
US7632476B2 (en) * | 2006-03-09 | 2009-12-15 | Praxair Technology, Inc. | Method of recovering carbon dioxide from a synthesis gas stream |
US7850944B2 (en) * | 2008-03-17 | 2010-12-14 | Air Products And Chemicals, Inc. | Steam-hydrocarbon reforming method with limited steam export |
-
2009
- 2009-12-16 IT ITMI2009A002199A patent/IT1398292B1/en active
-
2010
- 2010-12-15 WO PCT/EP2010/007772 patent/WO2011072877A1/en active Application Filing
- 2010-12-15 CA CA2783744A patent/CA2783744A1/en not_active Abandoned
- 2010-12-15 EP EP10792851A patent/EP2512980A1/en not_active Ceased
- 2010-12-15 RU RU2012126748/05A patent/RU2556671C2/en active
- 2010-12-15 US US13/516,482 patent/US20120301391A1/en not_active Abandoned
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1158617A (en) * | 1956-09-21 | 1958-06-17 | Azote & Prod Chim | Process for the preparation of gases rich in hydrogen by controlled catalytic oxidation of hydrocarbons |
US20040178124A1 (en) * | 2003-03-11 | 2004-09-16 | Ke Liu | Hydrogen desulfurizer for hydrocarbon feeds with separated adsorption and catalyst material |
US20050268554A1 (en) * | 2004-06-07 | 2005-12-08 | Ke Liu | Compact production of reformate and segregated H2, N2 and CO2 |
US20070122339A1 (en) * | 2005-11-28 | 2007-05-31 | General Electric Company | Methods and apparatus for hydrogen production |
US20070130831A1 (en) * | 2005-12-08 | 2007-06-14 | General Electric Company | System and method for co-production of hydrogen and electrical energy |
EP2072459A1 (en) * | 2007-11-21 | 2009-06-24 | ENI S.p.A. | Enhanced process for the production of synthesis gas starting from oxygenated compounds deriving from biomasses |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9932229B2 (en) | 2011-07-26 | 2018-04-03 | Stamicarbon B.V. | Method and system for production of hydrogen rich gas mixtures |
EP2736840B1 (en) * | 2011-07-26 | 2019-05-08 | Stamicarbon B.V. acting under the name of MT Innovation Center | Method for production of hydrogen rich gas mixtures |
WO2013062415A1 (en) * | 2011-10-26 | 2013-05-02 | Stamicarbon B.V. Acting Under The Name Of Mt Innovation Center | Method for producing synthesis gas for methanol production |
US9102532B2 (en) | 2011-10-26 | 2015-08-11 | Stamicarbon B.V. | Method for producing synthesis gas for methanol production |
EA026825B1 (en) * | 2011-10-26 | 2017-05-31 | Стамикарбон Б.В. Эктин Андер Те Нейм Оф Мт Инновейшн Сентр | Method for producing synthesis gas for methanol production |
EP2794465B1 (en) | 2011-12-19 | 2018-07-18 | Stamicarbon B.V. acting under the name of MT Innovation Center | Process for producing ammonia and urea |
WO2016016257A1 (en) | 2014-07-29 | 2016-02-04 | Eni S.P.A. | Integrated sct-cpo/pox process for producing synthesis gas |
WO2016016253A1 (en) * | 2014-07-29 | 2016-02-04 | Eni S.P.A. | Integrated short contact time catalytic partial oxidation/gas heated reforming process for the production of synthesis gas |
WO2016016256A1 (en) * | 2014-07-29 | 2016-02-04 | Eni S.P.A. | Integrated sct-cpo/atr process for the production of synthesis gas |
WO2016016251A1 (en) | 2014-07-29 | 2016-02-04 | Eni S.P.A. | Integrated sct-cpo/sr process for producing synthesis gas |
US10435343B2 (en) | 2016-04-13 | 2019-10-08 | Northwestern University | Efficient catalytic greenhouse gas-free hydrogen and aldehyde formation from alcohols |
EP3844135B1 (en) | 2018-08-29 | 2022-08-24 | ENI S.p.A. | Method and system for synthesizing methanol |
LU102057B1 (en) | 2020-09-09 | 2022-03-09 | Wurth Paul Sa | Method for operating a blast furnace installation |
WO2022053537A1 (en) | 2020-09-09 | 2022-03-17 | Paul Wurth S.A. | Method for operating a blast furnace installation |
IT202100011189A1 (en) | 2021-05-03 | 2022-11-03 | Nextchem S P A | LOW ENVIRONMENTAL IMPACT PROCESS FOR THE REDUCTION OF IRON MINERALS IN A BLAST FURNACE USING SYNTHETIC GAS |
WO2022233769A1 (en) | 2021-05-03 | 2022-11-10 | NextChem S.p.A. | Process utilizing synthesis gas for improving the environmental impact of the reduction of iron ore in blast furnaces |
IT202100012551A1 (en) | 2021-05-14 | 2022-11-14 | Rosetti Marino S P A | CO2 CONVERSION PROCESS |
IT202100015473A1 (en) | 2021-06-14 | 2022-12-14 | Nextchem S P A | METHOD OF PRODUCTION OF CATALYST FOR HIGH TEMPERATURE CHEMICAL PROCESSES AND THE CATALYST OBTAINED THUS |
WO2022263409A1 (en) | 2021-06-14 | 2022-12-22 | NextChem S.p.A. | Method for producing catalysts for high temperature chemical processes and catalysts thus obtained. |
LU500764B1 (en) | 2021-10-19 | 2023-04-20 | Wurth Paul Sa | Method for reducing carbon footprint in operating a metallurgical plant for producing pig iron |
WO2024165142A1 (en) | 2023-02-07 | 2024-08-15 | NextChem S.p.A. | Process of direct reduction of iron ores by means of synthesis gas produced with catalytic partial oxidation |
Also Published As
Publication number | Publication date |
---|---|
RU2556671C2 (en) | 2015-07-10 |
RU2012126748A (en) | 2014-01-27 |
ITMI20092199A1 (en) | 2011-06-17 |
CA2783744A1 (en) | 2011-06-23 |
EP2512980A1 (en) | 2012-10-24 |
IT1398292B1 (en) | 2013-02-22 |
US20120301391A1 (en) | 2012-11-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20120301391A1 (en) | Process for the production of hydrogen starting from liquid hydrocarbons, gaseous hydrocarbons and/or oxygenated compounds also deriving from biomasses | |
Rostrup-Nielsen | Production of synthesis gas | |
US9132402B2 (en) | Apparatus, systems, and processes for producing syngas and products therefrom | |
CA2507922C (en) | Autothermal reformer-reforming exchanger arrangement for hydrogen production | |
EP2566810B1 (en) | Process for the production of syngas and hydrogen starting from reagents comprising liquid hydrocarbons, gaseous hydrocarbons, and/or oxygenated compounds, also deriving from biomasses, by means of a non-integrated membrane reactor | |
EP1977993B1 (en) | Catalytic steam reforming with recycle | |
US20040170559A1 (en) | Hydrogen manufacture using pressure swing reforming | |
US20040191166A1 (en) | Hydrogen manufacture using pressure swing reforming | |
CN107021454B (en) | Method for producing hydrogen | |
CA3178048A1 (en) | Process for producing hydrogen | |
US9701535B2 (en) | Process for producing a syngas intermediate suitable for the production of hydrogen | |
Mosca et al. | Hydrogen in chemical and petrochemical industry | |
EP2697856A1 (en) | Non-catalytic recuperative reformer | |
AU2023232982A1 (en) | Process for producing hydrogen and method of retrofitting a hydrogen production unit | |
KR20240111741A (en) | How to retrofit a hydrogen production unit | |
GB2614780A (en) | Method for retrofitting a hydrogen production unit | |
US9803153B2 (en) | Radiant non-catalytic recuperative reformer | |
GB2620463A (en) | Process for producing hydrogen and method of retrofitting a hydrogen production unit | |
GB2625646A (en) | Process for producing hydrogen | |
Maxwell | Hydrogen Production | |
CN118451039A (en) | Method for producing hydrogen |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10792851 Country of ref document: EP Kind code of ref document: A1 |
|
DPE2 | Request for preliminary examination filed before expiration of 19th month from priority date (pct application filed from 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10792851 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2783744 Country of ref document: CA |
|
REEP | Request for entry into the european phase |
Ref document number: 2010792851 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010792851 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012126748 Country of ref document: RU |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13516482 Country of ref document: US |