WO2020187583A1 - Process for the production of urea formaldehyde concentrate - Google Patents

Process for the production of urea formaldehyde concentrate Download PDF

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Publication number
WO2020187583A1
WO2020187583A1 PCT/EP2020/055861 EP2020055861W WO2020187583A1 WO 2020187583 A1 WO2020187583 A1 WO 2020187583A1 EP 2020055861 W EP2020055861 W EP 2020055861W WO 2020187583 A1 WO2020187583 A1 WO 2020187583A1
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methanol
synthesis gas
ammonia
urea
carbon dioxide
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French (fr)
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Marcus SYMRENG
Pat A Han
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Topsoe AS
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Haldor Topsoe AS
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Priority to CN202080021485.6A priority Critical patent/CN113727964A/en
Priority to US17/420,025 priority patent/US11873268B2/en
Priority to AU2020244047A priority patent/AU2020244047B2/en
Publication of WO2020187583A1 publication Critical patent/WO2020187583A1/en
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
    • C07C273/04—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds from carbon dioxide and ammonia
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    • 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; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/025—Preparation or purification of gas mixtures for ammonia synthesis
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    • 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; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/382—Processes with two or more reaction steps, of which at least one is catalytic, e.g. steam reforming and partial oxidation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis
    • C01C1/0405—Preparation of ammonia by synthesis from N2 and H2 in presence of a catalyst
    • C01C1/0488—Processes integrated with preparations of other compounds, e.g. methanol, urea or with processes for power generation
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
    • C07C273/10—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds combined with the synthesis of ammonia
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/1516—Multisteps
    • C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/152—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the reactor used
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
    • C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
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    • 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
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
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    • 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
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    • 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
    • C01B2203/0435—Catalytic purification
    • C01B2203/0445—Selective methanation
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    • 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
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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    • C01B2203/061—Methanol production
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    • C01—INORGANIC CHEMISTRY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/068—Ammonia synthesis
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a process for the produc tion of urea formaldehyde concentrate from a hydrocarbon feed feedstock.
  • the invention is concerned with a paral lel co-production process for the production of methanol and urea product from a hydrocarbon containing feedstock by means of primary and secondary reforming, intermediary methanol and ammonia formation and conversion of the ammo nia to urea product and catalytic oxidation of methanol to formaldehyde .
  • the invention provides a process for the pro duction of urea formaldehyde concentrate from a hydrocarbon feedstock comprising steps of:
  • step (a) producing a synthesis gas containing hydrogen, carbon monoxide and dioxide and nitrogen by steam reforming the hydrocarbon feedstock in a primary reforming stage and sub sequently in a secondary reforming stage; (b) splitting the synthesis gas from step (a) into a metha nol synthesis gas and an ammonia synthesis gas;
  • step (c) subjecting the ammonia synthesis gas from step (b) in series to a high temperature water gas shift and a low tem perature water gas shift conversion;
  • step (d) removing at least part of the carbon dioxide from the ammonia synthesis gas from step (c) to obtain a carbon di- oxide depleted ammonia synthesis gas;
  • step (e) subjecting a carbon dioxide depleted ammonia synthesis gas from step (d) to catalytic methanation to remove the unconverted carbon monoxide to obtain a purified ammonia synthesis gas;
  • step (f) catalytically converting the nitrogen and hydrogen in the purified ammonia synthesis gas from step (e) in an am monia synthesis stage and withdrawing an effluent contain- ing ammonia;
  • step (g) passing at least part of the ammonia containing efflu ent to an urea synthesis stage and converting the ammonia in the effluent to urea product by reaction with at least part of the carbon dioxide being removed from the synthesis gas in step (d) ,
  • step (h) catalytically converting the carbon monoxide, carbon dioxide and hydrogen of the methanol synthesis gas from step (b) in a once-through methanol synthesis stage and withdrawing an effluent containing methanol and an effluent containing nitrogen, hydrogen and unconverted carbon monox ide and carbon dioxide;
  • step (i) recycling the effluent containing nitrogen, hydrogen and un-converted carbon monoxide and carbon dioxide to a fuel header as fuel to the primary reforming stage in step (a) and/or to the low temperature shift conversion in step (c) ;
  • step (j) subjecting the effluent containing methanol to distil lation and withdrawing purified methanol from the distilla tion;
  • step (k) oxidizing at least a part of the purified methanol from step (j) to formaldehyde;
  • step (l) absorbing the formaldehyde from step (k) in an absorber with water and an aqueous urea solution prepared from the urea product in step (g) to obtain the urea formaldehyde concentrate.
  • the term "primary reforming stage” means re forming being conducted in a conventional steam methane re former (SMR) , i.e. tubular reformer with the heat required for the endothermic reforming being provided by radiation heat from burners, such as burners arranged along the walls of the tubular reformer.
  • SMR steam methane re former
  • At least part of the fuel to the burners in the primary re- forming stage is provided by the effluent containing nitro gen, hydrogen and un-converted carbon monoxide and carbon dioxide recycled from the methanol synthesis.
  • second reforming stage means reforming being conducted in an autothermal reformer or catalytic partial oxidation reactor.
  • Suitable hydrocarbon feed stocks for use in the invention include methane, natural gas, LPG, naphtha and higher hy- drocarbons .
  • the hydrocarbon feedstock comprises methane, for instance in the form of natural gas, liquefied natural gas (LNG) or substitute natural gas (SNG) .
  • LNG liquefied natural gas
  • SNG substitute natural gas
  • preferred When employing naphtha and higher hydrocarbons, it is pre ferred to subject these feedstocks to a prereforming step prior to the primary reforming stage.
  • prereforming can be employed for all types of hydrocarbon feed stock.
  • the secondary reforming is conducted in a secondary reform er or autothermal reformer fed with air or oxygen enriched air in order to provide the required amount of nitrogen for the ammonia synthesis and the required amount of carbon monoxide, carbon dioxide and hydrogen for the methanol syn thesis together with required amount of carbon dioxide nec- essary for the conversion of ammonia to urea.
  • Removal of carbon dioxide from the ammonia synthesis gas may be performed by any conventional means in a physical or chemical wash as known in the art.
  • carbon dioxide removal is performed by the OASE process available from BASF, which allows easy recovery of absorbed carbon dioxide for use in the urea synthesis.
  • the methanol synthesis stage is preferably conducted by passing the synthesis gas at moderate pressure, such as 30- 60 bar and temperatures 150-300°C through at least one methanol reactor containing at least one, but preferably two fixed beds of methanol catalyst.
  • a particularly pre ferred methanol reactor is a fixed bed reactor cooled by a suitable cooling agent such as boiling water, e.g. boiling water reactor (BWR) .
  • BWR boiling water reactor
  • step (h) the methanol rich effluent is preferably a liq uid effluent. This effluent is obtained by cooling and con densation of the effluent gas from the methanol reactors.
  • the process of the invention may further com prise cooling the synthesis gas withdrawn from each metha nol reactor to condense methanol and passing the gas through a separator, withdrawing a bottom fraction from the separator containing the raw methanol, withdrawing an over- head fraction containing un-converted synthesis gas which is either passed to the fuel header as fuel for the primary reformer burners and/or the low temperature shift conver sion for boosting the hydrogen concentration in the shifted ammonia synthesis gas.
  • the effluent gas is added to the LTS with the aid of an ejector, where the main flow from the HTS acts as a motive flow and the effluent the suction flow.
  • the effluent is added upstream the LTS via a booster compres- sor/blower which increases the effluent pressure to fit the main process gas flow.
  • methanol reactor encompasses adiabatic fixed bed reactors and cooled reactors such as boiling water reactors and reactors of the condensing-methanol type which comprises within a common shell a fixed bed of methanol catalyst particles and cooling means adapted to indirectly cooling the methanol synthesis gas with a cooling agent.
  • step (e) the catalytic methanation stage for conversion of carbon monoxide to methane is conducted in at least one methanation reactor, which is preferably an adiabatic reac tor containing a fixed bed of methanation catalyst.
  • step (f) the ammonia synthesis gas from the methanation stage containing the correct proportion of hydrogen and ni trogen (3 ⁇ 4:N2 molar ratio of 3:1) is optionally passed through a compressor to obtain the required ammonia synthe sis pressure, such as 120 to 250 bar, preferably about 190 bar.
  • Ammonia is then produced in a conventional manner by means of an ammonia synthesis loop comprising at least one ammonia converter. Ammonia may be recovered from the efflu ent containing ammonia as liquid ammonia by condensation and subsequent separation.
  • a purge-gas stream containing hydrogen, nitrogen, ammonia and various inerts from step (f) is sent to a recovering unit, where the hydrogen is returned to the synthesis gas com pressor in step (f) and the ammonia is recovered and sent to the ammonia product stream.
  • the cleaned purge gas is sent to the reformer fuel header where it is used as fuel in step (a), i.e. it is returned as off-gas fuel to the re forming section of the plant, specifically to the primary reforming stage.
  • the ammonia being withdrawn from the ammonia synthesis is then converted to the urea product by reaction with carbon dioxide recovered from step (d) as described above.
  • To produce the formaldehyde employed in the preparation of the urea formaldehyde concentrate at least a part of the purified methanol withdrawn from the distillation in step (j) is sent to a formaldehyde unit (k), where the methanol is either preheated and quenched into preheated air, or evaporated and mixed with the preheated air, before it is oxidized over an oxidation catalyst to formaldehyde.
  • (k) is subsequently passed into a formaldehyde absorber.
  • the formaldehyde absorber the gaseous formaldehyde efflu ent from the oxidation step absorbed in water and aqueous urea suspension to form a Urea Formaldehyde Concentrate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Analytical Chemistry (AREA)
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Abstract

Parallel co-production process for the production of methanol and urea product from a hydrocarbon containing feed-stock by means of primary and secondary reforming, intermediary methanol and ammonia formation and conversion of the ammonia to urea product and catalytic oxidation of methanol to formaldehyde.

Description

Title: Process for the production of urea formaldehyde con- centrate
The present invention relates to a process for the produc tion of urea formaldehyde concentrate from a hydrocarbon feed feedstock.
More particularly the invention is concerned with a paral lel co-production process for the production of methanol and urea product from a hydrocarbon containing feedstock by means of primary and secondary reforming, intermediary methanol and ammonia formation and conversion of the ammo nia to urea product and catalytic oxidation of methanol to formaldehyde .
Production of urea by conversion of ammonia and carbon di oxide is a well-known process and conventionally employed in the industry.
It is the general object of the invention to provide a cost effective, simple and robust process for the production of urea formaldehyde concentrate in a unit that requires a minimum of equipment and unit operations.
Accordingly, the invention provides a process for the pro duction of urea formaldehyde concentrate from a hydrocarbon feedstock comprising steps of:
(a) producing a synthesis gas containing hydrogen, carbon monoxide and dioxide and nitrogen by steam reforming the hydrocarbon feedstock in a primary reforming stage and sub sequently in a secondary reforming stage; (b) splitting the synthesis gas from step (a) into a metha nol synthesis gas and an ammonia synthesis gas;
(c) subjecting the ammonia synthesis gas from step (b) in series to a high temperature water gas shift and a low tem perature water gas shift conversion;
(d) removing at least part of the carbon dioxide from the ammonia synthesis gas from step (c) to obtain a carbon di- oxide depleted ammonia synthesis gas;
(e) subjecting a carbon dioxide depleted ammonia synthesis gas from step (d) to catalytic methanation to remove the unconverted carbon monoxide to obtain a purified ammonia synthesis gas;
(f) catalytically converting the nitrogen and hydrogen in the purified ammonia synthesis gas from step (e) in an am monia synthesis stage and withdrawing an effluent contain- ing ammonia; and
(g) passing at least part of the ammonia containing efflu ent to an urea synthesis stage and converting the ammonia in the effluent to urea product by reaction with at least part of the carbon dioxide being removed from the synthesis gas in step (d) ,
(h) catalytically converting the carbon monoxide, carbon dioxide and hydrogen of the methanol synthesis gas from step (b) in a once-through methanol synthesis stage and withdrawing an effluent containing methanol and an effluent containing nitrogen, hydrogen and unconverted carbon monox ide and carbon dioxide;
(i) recycling the effluent containing nitrogen, hydrogen and un-converted carbon monoxide and carbon dioxide to a fuel header as fuel to the primary reforming stage in step (a) and/or to the low temperature shift conversion in step (c) ; (j) subjecting the effluent containing methanol to distil lation and withdrawing purified methanol from the distilla tion;
(k) oxidizing at least a part of the purified methanol from step (j) to formaldehyde;
(l) absorbing the formaldehyde from step (k) in an absorber with water and an aqueous urea solution prepared from the urea product in step (g) to obtain the urea formaldehyde concentrate.
In the operation of the methanol synthesis in a once- through synthesis is as mentioned above that a synthesis gas compressor is not necessary for the methanol synthesis. The benefit of avoiding compression is that is saving of CAPEX wise by not including a compressor in the methanol synthesis. It will make the process easier as there is less maintenance required and there are fewer rotating equip ments that might fail and trip the plant. This is very ad vantageous in a small plant as a compressor would be a big part of the investment. As used herein the term "primary reforming stage" means re forming being conducted in a conventional steam methane re former (SMR) , i.e. tubular reformer with the heat required for the endothermic reforming being provided by radiation heat from burners, such as burners arranged along the walls of the tubular reformer.
As an advantage of the process according to the invention, at least part of the fuel to the burners in the primary re- forming stage is provided by the effluent containing nitro gen, hydrogen and un-converted carbon monoxide and carbon dioxide recycled from the methanol synthesis.
As also used herein the term "secondary reforming stage" means reforming being conducted in an autothermal reformer or catalytic partial oxidation reactor.
Suitable hydrocarbon feed stocks for use in the invention include methane, natural gas, LPG, naphtha and higher hy- drocarbons .
Preferably, the hydrocarbon feedstock comprises methane, for instance in the form of natural gas, liquefied natural gas (LNG) or substitute natural gas (SNG) .
When employing naphtha and higher hydrocarbons, it is pre ferred to subject these feedstocks to a prereforming step prior to the primary reforming stage. However, prereforming can be employed for all types of hydrocarbon feed stock.
The secondary reforming is conducted in a secondary reform er or autothermal reformer fed with air or oxygen enriched air in order to provide the required amount of nitrogen for the ammonia synthesis and the required amount of carbon monoxide, carbon dioxide and hydrogen for the methanol syn thesis together with required amount of carbon dioxide nec- essary for the conversion of ammonia to urea.
Final control of the carbon monoxide/carbon dioxide ratio to meet the required amount of nitrogen, carbon monoxide, carbon dioxide and hydrogen for ammonia synthesis together with required amount of carbon dioxide necessary for the conversion of ammonia to urea, is obtained by subjecting the ammmonia synthesis gas to the high temperature and low temperature water gas shift reaction prior to the removal of carbon dioxide in step (d) .
Removal of carbon dioxide from the ammonia synthesis gas may be performed by any conventional means in a physical or chemical wash as known in the art. Preferably, carbon dioxide removal is performed by the OASE process available from BASF, which allows easy recovery of absorbed carbon dioxide for use in the urea synthesis.
The methanol synthesis stage is preferably conducted by passing the synthesis gas at moderate pressure, such as 30- 60 bar and temperatures 150-300°C through at least one methanol reactor containing at least one, but preferably two fixed beds of methanol catalyst. A particularly pre ferred methanol reactor is a fixed bed reactor cooled by a suitable cooling agent such as boiling water, e.g. boiling water reactor (BWR) . In step (h) the methanol rich effluent is preferably a liq uid effluent. This effluent is obtained by cooling and con densation of the effluent gas from the methanol reactors. Accordingly the process of the invention may further com prise cooling the synthesis gas withdrawn from each metha nol reactor to condense methanol and passing the gas through a separator, withdrawing a bottom fraction from the separator containing the raw methanol, withdrawing an over- head fraction containing un-converted synthesis gas which is either passed to the fuel header as fuel for the primary reformer burners and/or the low temperature shift conver sion for boosting the hydrogen concentration in the shifted ammonia synthesis gas.
The effluent gas is added to the LTS with the aid of an ejector, where the main flow from the HTS acts as a motive flow and the effluent the suction flow. Alternatively, the effluent is added upstream the LTS via a booster compres- sor/blower which increases the effluent pressure to fit the main process gas flow.
It would be understood that the term "methanol reactor" as used herein encompasses adiabatic fixed bed reactors and cooled reactors such as boiling water reactors and reactors of the condensing-methanol type which comprises within a common shell a fixed bed of methanol catalyst particles and cooling means adapted to indirectly cooling the methanol synthesis gas with a cooling agent.
In step (e) the catalytic methanation stage for conversion of carbon monoxide to methane is conducted in at least one methanation reactor, which is preferably an adiabatic reac tor containing a fixed bed of methanation catalyst.
In step (f) the ammonia synthesis gas from the methanation stage containing the correct proportion of hydrogen and ni trogen (¾:N2 molar ratio of 3:1) is optionally passed through a compressor to obtain the required ammonia synthe sis pressure, such as 120 to 250 bar, preferably about 190 bar. Ammonia is then produced in a conventional manner by means of an ammonia synthesis loop comprising at least one ammonia converter. Ammonia may be recovered from the efflu ent containing ammonia as liquid ammonia by condensation and subsequent separation. In order to improve the energy efficiency of the process a purge-gas stream containing hydrogen, nitrogen, ammonia and various inerts from step (f) is sent to a recovering unit, where the hydrogen is returned to the synthesis gas com pressor in step (f) and the ammonia is recovered and sent to the ammonia product stream. The cleaned purge gas is sent to the reformer fuel header where it is used as fuel in step (a), i.e. it is returned as off-gas fuel to the re forming section of the plant, specifically to the primary reforming stage.
The ammonia being withdrawn from the ammonia synthesis is then converted to the urea product by reaction with carbon dioxide recovered from step (d) as described above. To produce the formaldehyde employed in the preparation of the urea formaldehyde concentrate, at least a part of the purified methanol withdrawn from the distillation in step (j) is sent to a formaldehyde unit (k), where the methanol is either preheated and quenched into preheated air, or evaporated and mixed with the preheated air, before it is oxidized over an oxidation catalyst to formaldehyde.
The formaldehyde produced in the methanol oxidation step
(k) is subsequently passed into a formaldehyde absorber. In the formaldehyde absorber, the gaseous formaldehyde efflu ent from the oxidation step absorbed in water and aqueous urea suspension to form a Urea Formaldehyde Concentrate.
A major part of the effluent gas leaving the absorber top is sent back to the preheated air in (k), while the rest is preheated and catalytically incinerated in an incinerator reactor before it is purged to avoid build-up of inerts.

Claims

1. Process for the production of urea formaldehyde con centrate from a hydrocarbon feedstock comprising steps of:
(a) producing a synthesis gas containing hydrogen, carbon monoxide and dioxide and nitrogen by steam reforming the hydrocarbon feedstock in a primary reforming stage and sub sequently in a secondary reforming stage;
(b) splitting the synthesis gas from step (a) into a metha nol synthesis gas and an ammonia synthesis gas;
(c) subjecting the ammonia synthesis gas from step (b) in series to a high temperature water gas shift and a low tem perature water gas shift conversion;
(d) removing at least part of the carbon dioxide from the ammonia synthesis gas from step (c) to obtain a carbon di- oxide depleted ammonia synthesis gas;
(e) subjecting a carbon dioxide depleted ammonia synthesis gas from step (d) to catalytic methanation to remove the unconverted carbon monoxide to obtain a purified ammonia synthesis gas;
(f) catalytically converting the nitrogen and hydrogen in the purified ammonia synthesis gas from step (e) in an am monia synthesis stage and withdrawing an effluent contain ing ammonia; and (g) passing at least part of the ammonia containing efflu ent to an urea synthesis stage and converting the ammonia in the effluent to urea product by reaction with at least part of the carbon dioxide being removed from the synthesis gas in step (d) ,
(h) catalytically converting the carbon monoxide, carbon dioxide and hydrogen of the methanol synthesis gas from step (b) in a once-through methanol synthesis stage and withdrawing an effluent containing methanol and an effluent containing nitrogen, hydrogen and unconverted carbon monox ide and carbon dioxide;
(i) recycling the effluent containing nitrogen, hydrogen and un-converted carbon monoxide and carbon dioxide to a fuel header as fuel to the primary reforming stage in step (a) and/or to the low temperature shift conversion in step (c) ; (j) subjecting the effluent containing methanol to distil lation and withdrawing purified methanol from the distilla tion;
(k) oxidizing at least a part of the purified methanol from step (j) to formaldehyde;
(l) absorbing the formaldehyde from step (k) in an absorber with water and an aqueous urea solution prepared from the urea product in step (g) to obtain the urea formaldehyde concentrate .
2. Process of claim 1, wherein the urea formaldehyde con centrate is admixed to urea pellets or granulate.
3. Process of claim 1 or 2, wherein the effluent contain- ing nitrogen, hydrogen and unconverted carbon monoxide and carbon dioxide is recycled to the low temperature shift conversion in step (c) by means of an ejector booster com pressor/blower .
4. Process according to any one of claims 1-3, wherein the methanol synthesis stage in step (h) is performed in at least one methanol reactor containing one or two fixed bed methanol catalyst.
PCT/EP2020/055861 2019-03-15 2020-03-05 Process for the production of urea formaldehyde concentrate Ceased WO2020187583A1 (en)

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US20190031604A1 (en) * 2015-12-18 2019-01-31 Johnson Matthey Public Limited Company Integrated process for the production of formaldehyde-stabilised urea

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DE4010602A1 (en) 1989-04-05 1990-10-11 Piesteritz Agrochemie METHOD FOR THE PUBLIC USE OF RESIDUAL GAS FROM A PRECIOUS GAS PLANT
NO310863B1 (en) 1999-11-19 2001-09-10 Norske Stats Oljeselskap Cogeneration of methanol and electric power
AP2014007727A0 (en) * 2012-01-04 2014-06-30 Haldor Topsoe As Co-production of methanol and urea
GB201502893D0 (en) * 2015-02-20 2015-04-08 Johnson Matthey Plc Process
GB201618121D0 (en) * 2016-10-26 2016-12-07 Johnson Matthey Public Limited Company Process
AU2018233670B2 (en) 2017-03-12 2022-04-28 Haldor Topsøe A/S Co-production of methanol, ammonia and urea

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US20190031604A1 (en) * 2015-12-18 2019-01-31 Johnson Matthey Public Limited Company Integrated process for the production of formaldehyde-stabilised urea

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