CN107098359B - A kind of low pressure ammonia synthesis technology of combined production of methanol - Google Patents

A kind of low pressure ammonia synthesis technology of combined production of methanol Download PDF

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CN107098359B
CN107098359B CN201710325395.6A CN201710325395A CN107098359B CN 107098359 B CN107098359 B CN 107098359B CN 201710325395 A CN201710325395 A CN 201710325395A CN 107098359 B CN107098359 B CN 107098359B
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ammonia
synthesis
ammonia synthesis
ruthenium
convertor
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CN107098359A (en
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江莉龙
林建新
倪军
林炳裕
林科
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FUJIAN SANJU FUDA FERTILIZER CATALYST NATIONAL ENGINEERING RESEARCH CENTER Co Ltd
CHEMICAL FERTILIZER CATALYST STATE ENGINEERING RESEARCH CENTER FUZHOU UNIV
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FUJIAN SANJU FUDA FERTILIZER CATALYST NATIONAL ENGINEERING RESEARCH CENTER Co Ltd
CHEMICAL FERTILIZER CATALYST STATE ENGINEERING RESEARCH CENTER FUZHOU UNIV
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    • 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 in the gas phase
    • C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
    • C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6527—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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 in the gas phase
    • C01C1/0405—Preparation of ammonia by synthesis in the gas phase 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
    • Y02P20/10—Process efficiency
    • 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
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • 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
    • 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

Abstract

The present invention provides a kind of low pressure ammonia synthesis technology of combined production of methanol, include the following steps: 1) to carry out cryogenic air separation unit to air, obtain nitrogen and oxygen, oxygen and natural gas carry out pure oxygen autothermal reforming, obtain containing CO and H2Gaseous mixture；2) CO and H will be contained2Gaseous mixture be divided into two strands, synthesizing methanol, another burst of progress electrolysis water separation obtain hydrogen under the effect of the catalyst for one；3) hydrogen and nitrogen are mixed into syngas for synthetic ammonia, and it is subjected to level-one ammonia synthesis, synthesis pressure 5-7MPa in the first ammonia convertor of filling ferrum-based catalyst；4) second level ammonia synthesis, synthesis pressure 4-6MPa are carried out from the second ammonia convertor that the gaseous mixture come out in first ammonia convertor enters filling ruthenium-based catalyst.Present invention accomplishes ammonia synthesis process to require, guarantees technique even running, also improves the utilization rate of ammonia convertor outlet ammonia net value and nitrogen and hydrogen, coproduction methanol.

Description

A kind of low pressure ammonia synthesis technology of combined production of methanol
Technical field
The invention belongs to ammonia synthesis technical fields, and in particular to a kind of low pressure ammonia synthesis technology of combined production of methanol.
Background technique
Ammonia is important one of inorganic chemical product, occupies an important position in national economy.Except liquefied ammonia can be directly as Outside fertilizer, the nitrogenous fertilizer agriculturally used, such as urea, ammonium nitrate, ammonium phosphate, ammonium chloride and it is various contain nitrogen composite fertilizer, be all Using ammonia as raw material.Therefore, synthesis ammonia plays a significant role national economy, and the world synthesizes hydrazine yield every year and has reached 100,000,000 tons More than, wherein being used to produce chemical fertilizer, 20% raw material as other chemical products there are about 80% ammonia.
It is well known that synthesis ammonia is directly synthesized under high temperature, high pressure and catalyst by nitrogen and hydrogen.German chemist is breathed out Uncle began one's study from 1902 directly synthesizes ammonia by nitrogen and hydrogen.It was applied for a patent in 1908, i.e. " round-robin method ".It is common at present Ammonia synthesis technology mainly there are several types of 1) isobaric techniques: water-coal-slurry gas under 8.5MPa, through desulfurization, transformation, decarburization, benefit After nitrogen, ammonia is synthesized at 7.5MPa；2) micro- pressing technology: the water-coal-slurry gas at 8.5MPa through desulfurization, transformation, decarburization, mends nitrogen Afterwards, micro- pressurization (being attached to the micro- pressurized segment of unstripped gas by systemic circulation machine) synthesizes ammonia to 9.0-10.0MPa；3) boosting technique: Water-coal-slurry gas under 5.0MPa after the purified benefit nitrogen of gas, boosts to 15-22MPa synthesis ammonia.
In above-mentioned several ammonia synthesis technologies, the ammonia synthesis stage carries out under a certain pressure, still, with ammonia synthesis The progress of reaction, the parameters in reaction process are led if temperature, pressure, reaction raw materials and ammonia level can change Cause the stability in entire ammonia synthesis stage low.In order to reduce drawbacks described above to the influence degree of ammonia synthesis, Chinese patent literature CN106315619A discloses a kind of low pressure ammonia synthesis technology of ferrum-based catalyst string ruthenium-based catalyst.The technology is arranged at least Iron based ammonia synthesis catalyst is arranged in the ammonia convertor of upstream along ammonia synthesis path in two concatenated ammonia convertors, in downstream ammonia Ruthenium-based catalyst is set in synthetic tower.By the way that different types of ammonia synthesis catalyst is arranged, ammino has been adapted to a certain extent At the variation of response parameter in the process, the stable operation in ammonia synthesis stage ensure that.
Above-mentioned technology more deacclimatizes the variation of response parameter from the angle of catalyst, to ensure the stabilization in ammonia synthesis stage Operation.But ammonia synthesis reaction is the balanced reaction carried out under high temperature, high pressure and catalyst, influence factor is numerous, only upper Iron based ammonia synthesis catalyst is set in trip ammonia convertor, ruthenium-based catalyst is set in the ammonia convertor of downstream, it is difficult to meet synthesis Ammonia process requirement, also result in ammonia convertor outlet ammonia net value it is not high, the utilization rate of nitrogen and hydrogen is relatively low.Therefore, how to mention Ammonia synthesis technology for the utilization rate of a kind of high outlet ammonia net value, high nitrogen and hydrogen is those skilled in the art's urgent need to resolve One technical problem.
Summary of the invention
Therefore, technical problem to be solved by the present invention lies in overcome exist in the prior art outlet ammonia net value it is not high, nitrogen The relatively low defect of the utilization rate of gas and hydrogen, and then a kind of high outlet ammonia net value, high nitrogen and hydrogen utilization ratio, low energy are provided The low pressure ammonia synthesis technology consume, to run smoothly.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows:
Low pressure ammonia synthesis technology provided by the present invention, includes the following steps:
1) cryogenic air separation unit being carried out to air, obtains nitrogen and oxygen, the oxygen and natural gas carry out pure oxygen autothermal reforming, It obtains containing CO and H2Gaseous mixture；
2) described it will contain CO and H2Gaseous mixture be divided into two strands, one synthesizing methanol under the effect of the catalyst, another stock Electrolysis water separation is carried out, hydrogen is obtained；
3) be in molar ratio (1.5-2.5) by the hydrogen and nitrogen: 1 is mixed to form syngas for synthetic ammonia, and will be described Syngas for synthetic ammonia carries out level-one ammonia synthesis, the conjunction of the level-one ammonia synthesis in the first ammonia convertor of filling ferrum-based catalyst It is 5-7MPa at pressure；
4) from the second ammonia convertor that the gaseous mixture come out in first ammonia convertor enters filling ruthenium-based catalyst Second level ammonia synthesis is carried out, the synthesis pressure of the second level ammonia synthesis is 4-6MPa.
Further, in step 1), the synthesis temperature of the methanol is 210-250 DEG C, synthesis pressure 5-6MPa；
It further include by described containing CO and H before electrolysis water separation2Gaseous mixture be passed through in waste heat boiler recycle heat Amount, and high steam is obtained, it is used for the step of being pressurized to the syngas for synthetic ammonia；
It further include collecting the separating obtained CO of the electrolysis water in step 2)2, and by its in the low pressure ammonia synthesis technology The ammonia of synthesis reacts, and obtains urea；
In step 3), the synthesis temperature of the level-one ammonia synthesis is 430-500 DEG C；
The air speed of the syngas for synthetic ammonia is 4000-6000h-1。
Further, in step 4), the synthesis temperature of the second level ammonia synthesis is 350-435 DEG C；
The air speed of the gaseous mixture is 5000-12000h-1。
Further, the top half of second ammonia convertor loads the ruthenium-based catalyst, and institute is loaded in lower half portion Ferrum-based catalyst is stated, the syngas for synthetic ammonia enters wherein from the lower half portion of first ammonia convertor.
Further, the number of first ammonia convertor is at least one；
The number of second ammonia convertor is at least one.
Further, it when the number of the first ammonia convertor is at least two, is connected in series between each ammonia convertor；When second When the number of ammonia convertor is at least two, it is connected in series between each ammonia convertor.
Further, further include to from second ammonia convertor come out gaseous mixture cool and recycle heat, Isolated liquefied ammonia and remaining gas, and the step of remaining gas and the syngas for synthetic ammonia are mixed.
Further, S < 5ppm, CO < 10ppm, CO in the syngas for synthetic ammonia2< 10ppm.
Further, the ruthenium-based catalyst, the component including following parts by weight:
Preferably, the active carbon is the active carbon of N doping.
Further, further include the component of following parts by weight:
6-9 parts of barium monoxide
3-9 parts of potassium oxide.
Further, the preparation method of the ruthenium-based catalyst, includes the following steps:
(1) by basic magnesium carbonate, active carbon, basic carbonate cerium, molybdenum oxide and tungsten oxide ground and mixed, or by alkali formula carbon Sour magnesium, active carbon, basic carbonate cerium, molybdenum oxide, tungsten oxide, potassium carbonate and barium carbonate ground and mixed collect mixture, and to institute It states mixture to be formed, obtains molding；
(2) by the molding be impregnated in ruthenium compound aqueous solution or urea-containing ruthenium compound aqueous solution in, institute After stating dipping, take out；
(3) molding after the dipping is restored under reducing atmosphere；
(4) molding after the reduction is roasted at 1600-2500 DEG C, obtains ruthenium system ammonia synthesis catalyst.
Further, the granularity of the mixture is 0.05-0.5mm.
Further, in step (2), the temperature of the dipping is 10-40 DEG C；
The ruthenium compound aqueous solution or the urea-containing ruthenium compound aqueous solution are potassium ruthenate and/or ruthenic acid sodium Aqueous solution, wherein the mass fraction of ruthenium compound is 8-15%；
The mass fraction of urea is 5-8% in the urea-containing ruthenium compound aqueous solution.
Further, in step (3), the reducing atmosphere is hydrogen atmosphere；
The temperature of the reduction is 300-400 DEG C, time 6-12h.
Further, the temperature of the roasting is 1800-2000 DEG C.
Preferably, described to be ground to ball milling；
The dipping is incipient impregnation.
Further, the ferrum-based catalyst is with mass ratio for (2-3): (1-2): 1 Fe3O4, FeO and K2O be activity at Point, with rare earth oxide and MgAl2O4For auxiliary agent.
Further, the content of active constituent is 2-5wt% in the ferrum-based catalyst, and rare earth oxide content is 0.1-0.2wt%, MgAl2O4Content is 0.1-0.2wt%；
The rare earth oxide is CeO.
Compared with prior art, there are following advantages by the present invention:
1) ammonia synthesis process is divided into two sections by low pressure ammonia synthesis technology provided by the embodiment of the present invention, specified pressure, Particular kind of catalyst, specific H-N ratio unstripped gas under carry out, not only meet ammonia synthesis process requirement, guarantee that technique is flat Steady operation also improves the utilization rate of ammonia convertor outlet ammonia net value and nitrogen and hydrogen；Furthermore every section is compared with low pressure It is carried out under power, greatly reduces the energy consumption of ammonia synthesis technology.After tested, ammonia convertor outlet ammonia net value is up to 14.2%, nitrogen Utilization rate is up to 85%, and hydrogen utilization ratio is up to 90%, and process operation is steady.
2) low pressure ammonia synthesis technology provided by the embodiment of the present invention, by limiting the synthesis temperature of level-one ammonia synthesis, closing The air speed of the air speed of ammonification unstripped gas, the synthesis temperature of second level ammonia synthesis, gaseous mixture, while guaranteeing technique even running, Outlet ammonia net value, nitrogen and hydrogen utilization ratio are improved to the maximum extent；Pass through the top half filling in the first ammonia convertor Ruthenium-based catalyst, lower half portion load ferrum-based catalyst, further improve outlet ammonia net value；Using pure oxygen autothermal reforming, benefit Hydrogen and carbon monoxide are generated with methane and oxidation reaction, is exothermic reaction in itself, without external heating.Pure oxygen is carried out again certainly Thermal transition obtains hydrogen, and CO is changed into CO2, opened with Hydrogen Separation, effectively removed CO and H2, obtained hydrogen purity is high.
3) low pressure ammonia synthesis technology provided by this bright embodiment, wherein ruthenium system ammonia synthesis catalyst, using ruthenium, aoxidizes Magnesium, active carbon, cerium oxide, molybdenum oxide and tungsten oxide, and limit the ratio between each component.Reducing, carbon content, raising carrier are steady While qualitative, using the mutual cooperation between each component, synergistic effect, the Viability reduction of ammino is not resulted in not only, is improved instead Ammino is Viability.It is 3:1, air speed 10000h in mixed gas H-N ratio through detecting-1, reaction pressure 10MPa, reaction Temperature is to reach 25% or more using the ammonia convertor outlet ammonia density of the ruthenium system ammonia synthesis catalyst at 425 DEG C；Contain in hydrogen Amount maintains 100h to be heated to 1000 DEG C under 25% atmosphere, further takes out carry out ammonia synthesis, and ammonia convertor exports ammonia density still It can reach 24% or more, show that it, with high heat resistance, and is not easy methanation；The dispersion degree of ruthenium metal active ingredient is high, It can reach 50% or more, finally improve the outlet ammonia density and stability of ammonia synthesis technology.
4) low pressure ammonia synthesis technology provided by the embodiment of the present invention, using the active carbon of N doping, and using oxidation Barium and potassium oxide, stability and the ammino for further increasing ruthenium system ammonia synthesis catalyst are Viability；Using specific preparation method, First by basic magnesium carbonate, active carbon, basic carbonate cerium, molybdenum oxide and tungsten oxide ground and mixed, alternatively, by basic magnesium carbonate, work Property charcoal, basic carbonate cerium, molybdenum oxide, tungsten oxide, potassium carbonate and barium carbonate ground and mixed, molding, make between each solid material mix It closes uniformly, conducive to the homogeneity for improving ingredient in ruthenium system ammonia synthesis catalyst；It is water-soluble that the molding is impregnated in ruthenium compound again In liquid or in urea-containing ruthenium compound aqueous solution, it is sufficiently submerged in ruthenium compound in each solid material；Then, hydrogen is used Ruthenium compound is reduced to simple substance ruthenium；Finally, the molding after reduction is roasted at 1600-2500 DEG C, in the process of roasting Middle basic magnesium carbonate, basic carbonate cerium, potassium carbonate and barium carbonate are changed into corresponding metal oxide, meanwhile, dioxy can be generated The duct of ruthenium system ammonia synthesis catalyst can have been dredged by changing carbon and basic group, carbon dioxide, and basic group then improves carrier Alkalinity changes carrier surface electron density and structure, and stability and the ammino for improving ruthenium system ammonia synthesis catalyst are Viability. High-temperature roasting also can activated carbon, played active carbon improve the active ability of ammonia synthesis.
5) low pressure ammonia synthesis technology provided by the embodiment of the present invention, the wherein preparation method of ruthenium system ammonia synthesis catalyst, First molding is impregnated in urea-containing ruthenium compound aqueous solution, in conjunction with subsequent high-temperature roasting, is urged the ammonia synthesis of ruthenium system Each ingredient, especially active carbon in agent, have carried out N doping, improve the stability and ammonia synthesis of ruthenium system ammonia synthesis catalyst Activity；Second ruthenium compound uses potassium ruthenate and/or ruthenic acid sodium, and basic carbonate cerium occurs redox reaction with it, reduces Ruthenium reduces subsequent hydrogen usage and Methanation, meanwhile, it is also added to alkali metal in ruthenium system ammonia synthesis catalyst, It is Viability to improve ammino；The binder added in three forming processes can volatilize in subsequent high temperature roasting process, dredging Carrier duct increases catalysis area.
6) low pressure ammonia synthesis technology provided by the embodiment of the present invention, wherein ferrum-based catalyst is used with extra fine quality ratio Fe3O4, FeO and K2O is active constituent, with rare earth oxide and MgAl2O4For auxiliary agent, during ammonia synthesis, MgAl2O4To N2It exerts one's influence, weakens its chemical bond；Then Fe3O4With FeO under the action of rare earth oxide, it can add Speed is to N2Electronics is conveyed, itrogen-to-nitrogen bonds is dismantled；Finally, generating ammonia in hydrogen ion in conjunction with the nitrogen of negative valency.Thus use above-mentioned iron Base catalyst improves outlet ammonia net value.
Specific embodiment
Technical solution of the present invention will be clearly and completely described below, it is clear that described embodiment is this hair Bright a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not having Every other embodiment obtained under the premise of creative work is made, shall fall within the protection scope of the present invention.
Embodiment 1
The low pressure ammonia synthesis technology for present embodiments providing a kind of combined production of methanol, includes the following steps:
1) cryogenic air separation unit being carried out to air, obtains nitrogen and oxygen, the oxygen and natural gas carry out pure oxygen autothermal reforming, It obtains containing CO and H2Gaseous mixture；Furthermore contain CO and H2Gaseous mixture be passed through in waste heat boiler and recycle heat, and obtain high pressure steaming Vapour is used for being pressurized the syngas for synthetic ammonia；Then, described it will contain CO and H2Gaseous mixture be divided into two strands, one Under the action of copper-based catalysts, the synthesizing methanol under 210 DEG C, 6MPa, another burst of progress electrolysis water separation obtains hydrogen；Finally, Electrolysis water separation is carried out to the gaseous mixture, obtains hydrogen；The hydrogen and nitrogen are mixed to form syngas for synthetic ammonia, wherein S < 5ppm, CO < 10ppm, CO2The molar ratio of < 10ppm, hydrogen and nitrogen is 1.7:1；
It 2) is 5000h with air speed by above-mentioned syngas for synthetic ammonia-1Filling ferrum-based catalyst the first ammonia convertor in into Row level-one ammonia synthesis, the synthesis pressure of the level-one ammonia synthesis is 6MPa, synthesis temperature is 450 DEG C；
Wherein, it is the Fe of 2:2:1 that the ferrum-based catalyst, which is with mass ratio,3O4, FeO and K2O is active constituent, with rare earth Element oxide CeO and MgAl2O4For auxiliary agent, the content of active constituent is 4wt%, rare earth element oxygen in the ferrum-based catalyst Compound content is 0.1wt%, MgAl2O4Content is 0.2wt%.
3) gaseous mixture come out from first ammonia convertor is with air speed 8000h-1Into the of filling ruthenium-based catalyst Second level ammonia synthesis is carried out in two ammonia convertors, the synthesis pressure of the second level ammonia synthesis is 5MPa, synthesis temperature is 380 DEG C；
Wherein, ruthenium system ammonia synthesis catalyst is by the ruthenium of 5g, the magnesia of 5g, the active carbon of 80g, the cerium oxide of 7g, 1.5g Molybdenum oxide and 1.5g tungsten oxide composition；
The preparation method of above-mentioned ruthenium system ammonia synthesis catalyst, includes the following steps:
(1) by basic magnesium carbonate, active carbon, basic carbonate cerium, molybdenum oxide and tungsten oxide ball milling mixing, collecting granularity is The mixture of 0.1mm, and add binder-epoxy resin into the mixture and formed, obtain molding；
(2) by the molding incipient impregnation in mass fraction be 12% potassium ruthenate aqueous solution in, control dipping Temperature be 25 DEG C, after dipping, take out；
(3) molding after the dipping is restored in hydrogen, the temperature for controlling reduction is 350 DEG C, and the time is 9h；
(4) molding after the reduction is roasted at 1900 DEG C, obtains ruthenium system ammonia synthesis catalyst.
Embodiment 2
The low pressure ammonia synthesis technology for present embodiments providing a kind of combined production of methanol, includes the following steps:
1) cryogenic air separation unit being carried out to air, obtains nitrogen and oxygen, the oxygen and natural gas carry out pure oxygen autothermal reforming, It obtains containing CO and H2Gaseous mixture；Furthermore contain CO and H2Gaseous mixture be passed through in waste heat boiler and recycle heat, and obtain high pressure steaming Vapour is used for being pressurized the syngas for synthetic ammonia；Then, described it will contain CO and H2Gaseous mixture be divided into two strands, one Under the action of copper-based catalysts, the synthesizing methanol under 250 DEG C, 5MPa, another burst of progress electrolysis water separation obtains hydrogen；Finally, Electrolysis water separation is carried out to the gaseous mixture, obtains hydrogen；The hydrogen and nitrogen are mixed to form syngas for synthetic ammonia, wherein S < 5ppm, CO < 10ppm, CO2The molar ratio of < 10ppm, hydrogen and nitrogen is 1.5:1；
It 2) is 6000h with air speed by above-mentioned syngas for synthetic ammonia-1Filling ferrum-based catalyst the first ammonia convertor in into Row level-one ammonia synthesis, the synthesis pressure of the level-one ammonia synthesis is 5MPa, synthesis temperature is 500 DEG C；
Wherein, it is the Fe of 3:1:1 that the ferrum-based catalyst, which is with mass ratio,3O4, FeO and K2O is active constituent, with rare earth Element oxide CeO and MgAl2O4For auxiliary agent, the content of active constituent is 2wt%, rare earth element oxygen in the ferrum-based catalyst Compound content is 0.2wt%, MgAl2O4Content is 0.1wt%；
3) gaseous mixture come out from first ammonia convertor is with air speed 12000h-1Into the of filling ruthenium-based catalyst Second level ammonia synthesis is carried out in two ammonia convertors, the synthesis pressure of the second level ammonia synthesis is 4MPa, synthesis temperature is 350 DEG C；
Wherein, ruthenium system ammonia synthesis catalyst is by the ruthenium of 2g, the magnesia of 8g, the active carbon of 70g, the cerium oxide of 3g, 2g The tungsten oxide of molybdenum oxide and 1g composition；
The preparation method of above-mentioned ruthenium system ammonia synthesis catalyst, includes the following steps:
(1) by basic magnesium carbonate, active carbon, basic carbonate cerium, molybdenum oxide and tungsten oxide ball milling mixing, collecting granularity is The mixture of 0.05mm, and the mixture is formed, obtain molding；
(2) by the molding incipient impregnation in mass fraction be 8% ruthenic acid sodium aqueous solution in, control dipping Temperature is 40 DEG C, after dipping, is taken out；
(3) molding after the dipping is restored in hydrogen, the temperature for controlling reduction is 300 DEG C, and the time is 12h；
(4) molding after the reduction is roasted at 2500 DEG C, obtains ruthenium system ammonia synthesis catalyst.
Embodiment 3
The low pressure ammonia synthesis technology for present embodiments providing a kind of combined production of methanol, includes the following steps:
1) cryogenic air separation unit being carried out to air, obtains nitrogen and oxygen, the oxygen and natural gas carry out pure oxygen autothermal reforming, It obtains containing CO and H2Gaseous mixture；Furthermore contain CO and H2Gaseous mixture be passed through in waste heat boiler and recycle heat, and obtain high pressure steaming Vapour is used for being pressurized the syngas for synthetic ammonia；Then, described it will contain CO and H2Gaseous mixture be divided into two strands, one Under the action of copper-based catalysts, the synthesizing methanol under 230 DEG C, 5.5MPa, another burst of progress electrolysis water separation obtains hydrogen；Most Afterwards, electrolysis water separation is carried out to the gaseous mixture, obtains hydrogen；The hydrogen and nitrogen are mixed to form syngas for synthetic ammonia, Wherein S < 5ppm, CO < 10ppm, CO2The molar ratio of < 10ppm, hydrogen and nitrogen is 2.5:1；
It 2) is 4000h with air speed by above-mentioned syngas for synthetic ammonia-1Filling ferrum-based catalyst the first ammonia convertor in into Row level-one ammonia synthesis, the synthesis pressure of the level-one ammonia synthesis is 7MPa, synthesis temperature is 430 DEG C；
Wherein, it is the Fe of 2.5:1.5:1 that the ferrum-based catalyst, which is with mass ratio,3O4, FeO and K2O is active constituent, with Rare earth oxide CeO and MgAl2O4For auxiliary agent, the content of active constituent is 3wt%, rare earth member in the ferrum-based catalyst Plain oxide content is 0.15wt%, MgAl2O4Content is 0.1wt%；
3) gaseous mixture come out from first ammonia convertor is with air speed 5000h-1Into the of filling ruthenium-based catalyst Second level ammonia synthesis is carried out in two ammonia convertors, the synthesis pressure of the second level ammonia synthesis is 6MPa, synthesis temperature is 535 DEG C；
Wherein, the ruthenium system ammonia synthesis catalyst is by the ruthenium of 8g, the magnesia of 2g, the active carbon of 85g, the cerium oxide of 3g, 1g Molybdenum oxide and 2g tungsten oxide composition；
The preparation method of above-mentioned ruthenium system ammonia synthesis catalyst, includes the following steps:
(1) by basic magnesium carbonate, active carbon, basic carbonate cerium, molybdenum oxide and tungsten oxide ball milling mixing, collecting granularity is The mixture of 0.5mm, and the mixture is formed, obtain molding；
(2) by the molding incipient impregnation in mass fraction be 15% potassium ruthenate aqueous solution in, control dipping Temperature be 10 DEG C, after dipping, take out；
(3) molding after the dipping is restored in hydrogen, the temperature for controlling reduction is 400 DEG C, and the time is 6h；
(4) molding after the reduction is roasted at 1600 DEG C, obtains ruthenium system ammonia synthesis catalyst.
Embodiment 4
The low pressure ammonia synthesis technology for present embodiments providing a kind of combined production of methanol, includes the following steps:
1) cryogenic air separation unit being carried out to air, obtains nitrogen and oxygen, the oxygen and natural gas carry out pure oxygen autothermal reforming, It obtains containing CO and H2Gaseous mixture；Furthermore contain CO and H2Gaseous mixture be passed through in waste heat boiler and recycle heat, and obtain high pressure steaming Vapour is used for being pressurized the syngas for synthetic ammonia；Then, described it will contain CO and H2Gaseous mixture be divided into two strands, one Under the action of copper-based catalysts, the synthesizing methanol under 220 DEG C, 5MPa, another burst of progress electrolysis water separation obtains hydrogen；Finally, Electrolysis water separation is carried out to the gaseous mixture, obtains hydrogen；The hydrogen and nitrogen are mixed to form syngas for synthetic ammonia, wherein S < 5ppm, CO < 10ppm, CO2The molar ratio of < 10ppm, hydrogen and nitrogen is 1.5:1；
It 2) is 4500h with air speed by above-mentioned syngas for synthetic ammonia-1Filling ferrum-based catalyst the first ammonia convertor in into Row level-one ammonia synthesis, the synthesis pressure of the level-one ammonia synthesis is 5.5MPa, synthesis temperature is 460 DEG C；
Wherein, it is the Fe of 3:2:1 that the ferrum-based catalyst, which is with mass ratio,3O4, FeO and K2O is active constituent, with rare earth Element oxide CeO and MgAl2O4For auxiliary agent, the content of active constituent is 3wt%, rare earth element oxygen in the ferrum-based catalyst Compound content is 0.2wt%, MgAl2O4Content is 0.15wt%；
3) gaseous mixture come out from first ammonia convertor is with air speed 7000h-1Into the of filling ruthenium-based catalyst Second level ammonia synthesis is carried out in two ammonia convertors, the synthesis pressure of the second level ammonia synthesis is 5MPa, synthesis temperature is 400 DEG C；
Wherein, the ruthenium system ammonia synthesis catalyst by the ruthenium of 5g, the magnesia of 5g, the active carbon of 80g, 7g cerium oxide, The molybdenum oxide of 1.5g, the tungsten oxide of 1.5g, the barium monoxide of 8g and 7g potassium oxide composition；
The preparation method of above-mentioned ruthenium system ammonia synthesis catalyst, includes the following steps:
(1) basic magnesium carbonate, active carbon, basic carbonate cerium, molybdenum oxide, tungsten oxide, potassium carbonate and barium carbonate ball milling are mixed It closes, collects the mixture that granularity is 0.1mm, and add binder-epoxy resin into the mixture and formed, obtain Molding；
(2) by the molding incipient impregnation in mass fraction be 11% potassium ruthenate aqueous solution in, control dipping Temperature be 30 DEG C, after dipping, take out；
(3) molding after the dipping is restored in hydrogen, the temperature for controlling reduction is 350 DEG C, and the time is 9h；
(4) molding after the reduction is roasted at 1900 DEG C, obtains ruthenium system ammonia synthesis catalyst；
4) to from second ammonia convertor come out gaseous mixture cool and recycle heat, isolated liquefied ammonia and Remaining gas, and syngas for synthetic ammonia described in the remaining gas and step 1) is mixed.
Embodiment 5
The low pressure ammonia synthesis technology for present embodiments providing a kind of combined production of methanol, includes the following steps:
1) cryogenic air separation unit being carried out to air, obtains nitrogen and oxygen, the oxygen and natural gas carry out pure oxygen autothermal reforming, It obtains containing CO and H2Gaseous mixture；Furthermore contain CO and H2Gaseous mixture be passed through in waste heat boiler and recycle heat, and obtain high pressure steaming Vapour is used for being pressurized the syngas for synthetic ammonia；Then, described it will contain CO and H2Gaseous mixture be divided into two strands, one Under the action of copper-based catalysts, the synthesizing methanol under 230 DEG C, 6MPa, another burst of progress electrolysis water separation obtains hydrogen；Finally, Electrolysis water separation is carried out to the gaseous mixture, obtains hydrogen；The hydrogen and nitrogen are mixed to form syngas for synthetic ammonia, wherein S < 5ppm, CO < 10ppm, CO2The molar ratio of < 10ppm, hydrogen and nitrogen is 2:1；
It 2) is 6000h with air speed by above-mentioned syngas for synthetic ammonia-1Filling ferrum-based catalyst the first ammonia convertor in into Row level-one ammonia synthesis, the synthesis pressure of the level-one ammonia synthesis is 6.8MPa, synthesis temperature is 460 DEG C；
Wherein, it is the Fe of 2:1.5:1 that the ferrum-based catalyst, which is with mass ratio,3O4, FeO and K2O is active constituent, with dilute Earth elements oxide CeO and MgAl2O4For auxiliary agent, the content of active constituent is 3wt%, rare earth element in the ferrum-based catalyst Oxide content is 0.1wt%, MgAl2O4Content is 0.15wt%；
3) gaseous mixture come out from first ammonia convertor is with air speed 10000h-1Into the of filling ruthenium-based catalyst Second level ammonia synthesis is carried out in two ammonia convertors, the synthesis pressure of the second level ammonia synthesis is 6MPa, synthesis temperature is 360 DEG C；
Wherein, the ruthenium system ammonia synthesis catalyst is by the ruthenium of 2g, the magnesia of 8g, the active carbon of 70g, the cerium oxide of 3g, 2g Molybdenum oxide and 1g tungsten oxide composition；
The preparation method of above-mentioned ruthenium system ammonia synthesis catalyst, includes the following steps:
(1) by basic magnesium carbonate, active carbon, basic carbonate cerium, molybdenum oxide and tungsten oxide ball milling mixing, collecting granularity is The mixture of 0.05mm, and the mixture is formed, obtain molding；
(2) by the molding incipient impregnation in mass fraction be 8% urea-containing ruthenic acid sodium aqueous solution in, control The temperature of system dipping is 40 DEG C, and the mass fraction of urea is 7%, after dipping, is taken out；
(3) molding after the dipping is restored in hydrogen, the temperature for controlling reduction is 300 DEG C, and the time is 12h；
(4) molding after the reduction is roasted at 1800 DEG C, obtains ruthenium system ammonia synthesis catalyst.
4) to from second ammonia convertor come out gaseous mixture cool and recycle heat, isolated liquefied ammonia and Remaining gas, and syngas for synthetic ammonia described in the remaining gas and step 1) is mixed.
Embodiment 6
The low pressure ammonia synthesis technology for present embodiments providing a kind of combined production of methanol, includes the following steps:
1) cryogenic air separation unit being carried out to air, obtains nitrogen and oxygen, the oxygen and natural gas carry out pure oxygen autothermal reforming, It obtains containing CO and H2Gaseous mixture；Furthermore contain CO and H2Gaseous mixture be passed through in waste heat boiler and recycle heat, and obtain high pressure steaming Vapour is used for being pressurized the syngas for synthetic ammonia；Then, described it will contain CO and H2Gaseous mixture be divided into two strands, one Under the action of copper-based catalysts, the synthesizing methanol under 220 DEG C, 5MPa, another burst of progress electrolysis water separation obtains hydrogen；Finally, Electrolysis water separation is carried out to the gaseous mixture, obtains hydrogen；The hydrogen and nitrogen are mixed to form syngas for synthetic ammonia, wherein S < 5ppm, CO < 10ppm, CO2The molar ratio of < 10ppm, hydrogen and nitrogen is 2:1；
It 2) is 6000h with air speed by above-mentioned syngas for synthetic ammonia-1Into in the first ammonia convertor of filling ferrum-based catalyst Level-one ammonia synthesis is carried out, the synthesis pressure of the level-one ammonia synthesis is 5MPa, synthesis temperature is 450 DEG C；
Wherein, it is the Fe of 2:1.5:1 that the ferrum-based catalyst, which is with mass ratio,3O4, FeO and K2O is active constituent, with dilute Earth elements oxide CeO and MgAl2O4For auxiliary agent, the content of active constituent is 3wt%, rare earth element in the ferrum-based catalyst Oxide content is 0.1wt%, MgAl2O4Content is 0.2wt%；
3) gaseous mixture come out from second ammonia convertor is with air speed 7000h-1, the ruthenium base is loaded in top half Catalyst, lower half portion, which is loaded, carries out second level ammonia synthesis, the second level ammino in the first ammonia convertor of the ferrum-based catalyst At synthesis pressure be 4.5MPa, synthesis temperature is 350 DEG C；
Wherein, the ruthenium system ammonia synthesis catalyst is by the ruthenium of 8g, the magnesia of 2g, the active carbon of 85g, the cerium oxide of 9g, 1g Molybdenum oxide, the tungsten oxide of 2g, the barium monoxide of 6g and 9g potassium oxide composition；
The preparation method of above-mentioned ruthenium system ammonia synthesis catalyst, includes the following steps:
(1) basic magnesium carbonate, active carbon, basic carbonate cerium, molybdenum oxide, tungsten oxide, potassium carbonate and barium carbonate ball milling are mixed It closes, collects granularity and be the mixture of 0.5mm, and the mixture is formed, obtain molding；
(2) by the molding incipient impregnation in mass fraction be 15% urea-containing potassium ruthenate aqueous solution in, The temperature of control dipping is 10 DEG C, and the mass fraction of urea is 5%, after dipping, is taken out；
(3) molding after the dipping is restored in hydrogen, the temperature for controlling reduction is 400 DEG C, and the time is 6h；
(4) molding after the reduction is roasted at 1600 DEG C, obtains ruthenium system ammonia synthesis catalyst.
4) to from second ammonia convertor come out gaseous mixture cool and recycle heat, isolated liquefied ammonia and Remaining gas, and syngas for synthetic ammonia described in the remaining gas and step 1) is mixed.
Embodiment 7
The low pressure ammonia synthesis technology for present embodiments providing a kind of combined production of methanol, includes the following steps:
1) cryogenic air separation unit being carried out to air, obtains nitrogen and oxygen, the oxygen and natural gas carry out pure oxygen autothermal reforming, It obtains containing CO and H2Gaseous mixture；Furthermore contain CO and H2Gaseous mixture be passed through in waste heat boiler and recycle heat, and obtain high pressure steaming Vapour is used for being pressurized the syngas for synthetic ammonia；Then, described it will contain CO and H2Gaseous mixture be divided into two strands, one Under the action of copper-based catalysts, the synthesizing methanol under 230 DEG C, 6MPa, another burst of progress electrolysis water separation obtains hydrogen；Finally, Electrolysis water separation is carried out to the gaseous mixture, obtains hydrogen；The hydrogen and nitrogen are mixed to form syngas for synthetic ammonia, wherein S < 5ppm, CO < 10ppm, CO2The molar ratio of < 10ppm, hydrogen and nitrogen is 1.5:1；
It 2) is 7000h with air speed by above-mentioned syngas for synthetic ammonia-1In two concatenated first ammonia of filling ferrum-based catalyst Level-one ammonia synthesis is carried out in synthetic tower, the synthesis pressure of the level-one ammonia synthesis is 6MPa, synthesis temperature is 450 DEG C；
Wherein, it is the Fe of 3:2:1 that the ferrum-based catalyst, which is with mass ratio,3O4, FeO and K2O is active constituent, with rare earth Element oxide CeO and MgAl2O4For auxiliary agent, the content of active constituent is 3wt%, rare earth element oxygen in the ferrum-based catalyst Compound content is 0.2wt%, MgAl2O4Content is 0.2wt%；
3) gaseous mixture come out from first ammonia convertor is with air speed 8000h-1Into two concatenated filling ruthenium bases Second level ammonia synthesis is carried out in second ammonia convertor of catalyst, the synthesis pressure of the second level ammonia synthesis is 5.5MPa, synthesis is warm Degree is 400 DEG C；
Wherein, the ruthenium system ammonia synthesis catalyst by the ruthenium of 4g, the magnesia of 6g, the active carbon of 75g, 8g cerium oxide, The molybdenum oxide of 1.5g, the tungsten oxide of 1g, the barium monoxide of 9g and 3g potassium oxide composition；
The preparation method of above-mentioned ruthenium system ammonia synthesis catalyst, includes the following steps:
(1) basic magnesium carbonate, active carbon, basic carbonate cerium, molybdenum oxide, tungsten oxide, potassium carbonate and barium carbonate ball milling are mixed It closes, collects granularity and be the mixture of 0.2mm, and the mixture is formed, obtain molding；
(2) by the molding incipient impregnation in mass fraction be 9% urea-containing potassium ruthenate aqueous solution in, control The temperature of system dipping is 30 DEG C, and the mass fraction of urea is 8%, after dipping, is taken out；
(3) molding after the dipping is restored in hydrogen, the temperature for controlling reduction is 360 DEG C, and the time is 8h；
(4) molding after the reduction is roasted at 2100 DEG C, obtains ruthenium system ammonia synthesis catalyst.
4) to from second ammonia convertor come out gaseous mixture cool and recycle heat, isolated liquefied ammonia and Remaining gas, and syngas for synthetic ammonia described in the remaining gas and step 1) is mixed, it is separating obtained to collect the electrolysis water CO2, and it is reacted with liquefied ammonia, obtain urea.
Comparative example 1
This comparative example provides a kind of ammonia synthesis technology, includes the following steps:
1) cryogenic air separation unit being carried out to air, obtains nitrogen and oxygen, the oxygen and natural gas carry out pure oxygen autothermal reforming, It obtains containing CO and H2Gaseous mixture；Furthermore contain CO and H2Gaseous mixture be passed through in waste heat boiler and recycle heat, and obtain high pressure steaming Vapour is used for being pressurized the syngas for synthetic ammonia；Finally, carrying out electrolysis water separation to the gaseous mixture, hydrogen is obtained； The hydrogen and nitrogen are mixed to form syngas for synthetic ammonia, wherein S < 5ppm, CO < 10ppm, CO2< 10ppm, hydrogen with The molar ratio of nitrogen is 2.8:1；
It 2) is 5000h with air speed by above-mentioned syngas for synthetic ammonia-1Filling ferrum-based catalyst the first ammonia convertor in into Row level-one ammonia synthesis, the synthesis pressure of the level-one ammonia synthesis is 8MPa, synthesis temperature is 300 DEG C；
Wherein, it is the Fe of 2:2:1 that the ferrum-based catalyst, which is with mass ratio,3O4, FeO and K2O is active constituent, with rare earth Element oxide CeO and MgAl2O4For auxiliary agent, the content of active constituent is 4wt%, rare earth element oxygen in the ferrum-based catalyst Compound content is 0.1wt%, MgAl2O4Content is 0.2wt%.
3) gaseous mixture come out from first ammonia convertor is with air speed 8000h-1Into the of filling ruthenium-based catalyst Second level ammonia synthesis is carried out in two ammonia convertors, the synthesis pressure of the second level ammonia synthesis is 5MPa, synthesis temperature is 380 DEG C；
Wherein, ruthenium system ammonia synthesis catalyst is by the ruthenium of 5g, the magnesia of 5g, the active carbon of 80g, the cerium oxide of 7g, 1.5g Molybdenum oxide and 1.5g tungsten oxide composition；
The preparation method of above-mentioned ruthenium system ammonia synthesis catalyst, includes the following steps:
(1) by basic magnesium carbonate, active carbon, basic carbonate cerium, molybdenum oxide and tungsten oxide ball milling mixing, collecting granularity is The mixture of 0.1mm, and add binder-epoxy resin into the mixture and formed, obtain molding；
(2) by the molding incipient impregnation in mass fraction be 12% potassium ruthenate aqueous solution in, control dipping Temperature be 25 DEG C, after dipping, take out；
(3) molding after the dipping is restored in hydrogen, the temperature for controlling reduction is 350 DEG C, and the time is 9h；
(4) molding after the reduction is roasted at 1900 DEG C, obtains ruthenium system ammonia synthesis catalyst.
Comparative example 2
This comparative example provides a kind of ammonia synthesis technology, includes the following steps:
1) cryogenic air separation unit being carried out to air, obtains nitrogen and oxygen, the oxygen and natural gas carry out pure oxygen autothermal reforming, It obtains containing CO and H2Gaseous mixture；Furthermore contain CO and H2Gaseous mixture be passed through in waste heat boiler and recycle heat, and obtain high pressure steaming Vapour is used for being pressurized the syngas for synthetic ammonia；Finally, carrying out electrolysis water separation to the gaseous mixture, hydrogen is obtained；It will The hydrogen and nitrogen are mixed to form syngas for synthetic ammonia, wherein S < 5ppm, CO < 10ppm, CO2< 10ppm, hydrogen and nitrogen The molar ratio of gas is 1.5:1；
It 2) is 12000h with air speed by above-mentioned syngas for synthetic ammonia-1Filling ruthenium-based catalyst the first ammonia convertor in into Row level-one ammonia synthesis, the synthesis pressure of the level-one ammonia synthesis is 4MPa, synthesis temperature is 350 DEG C；
Wherein, ruthenium system ammonia synthesis catalyst is by the ruthenium of 2g, the magnesia of 8g, the active carbon of 70g, the cerium oxide of 3g, 2g The tungsten oxide of molybdenum oxide and 1g composition；
The preparation method of above-mentioned ruthenium system ammonia synthesis catalyst, includes the following steps:
(1) by basic magnesium carbonate, active carbon, basic carbonate cerium, molybdenum oxide and tungsten oxide ball milling mixing, collecting granularity is The mixture of 0.05mm, and the mixture is formed, obtain molding；
(2) by the molding incipient impregnation in mass fraction be 8% ruthenic acid sodium aqueous solution in, control dipping Temperature is 40 DEG C, after dipping, is taken out；
(3) molding after the dipping is restored in hydrogen, the temperature for controlling reduction is 300 DEG C, and the time is 12h；
(4) molding after the reduction is roasted at 2500 DEG C, obtains ruthenium system ammonia synthesis catalyst；
3) gaseous mixture come out from first ammonia convertor is with air speed 6000h-1Into the of filling ferrum-based catalyst Second level ammonia synthesis is carried out in two ammonia convertors, the synthesis pressure of the second level ammonia synthesis is 5MPa, synthesis temperature is 500 DEG C；
Wherein, it is the Fe of 3:1:1 that the ferrum-based catalyst, which is with mass ratio,3O4, FeO and K2O is active constituent, with rare earth Element oxide CeO and MgAl2O4For auxiliary agent, the content of active constituent is 2wt%, rare earth element oxygen in the ferrum-based catalyst Compound content is 0.2wt%, MgAl2O4Content is 0.1wt%；
Comparative example 3
This comparative example provides a kind of ammonia synthesis technology, includes the following steps:
1) cryogenic air separation unit being carried out to air, obtains nitrogen and oxygen, the oxygen and natural gas carry out pure oxygen autothermal reforming, It obtains containing CO and H2Gaseous mixture；Furthermore contain CO and H2Gaseous mixture be passed through in waste heat boiler and recycle heat, and obtain high pressure steaming Vapour is used for being pressurized the syngas for synthetic ammonia；Finally, carrying out electrolysis water separation to the gaseous mixture, hydrogen is obtained；It will The hydrogen and nitrogen are mixed to form syngas for synthetic ammonia, wherein S < 5ppm, CO < 10ppm, CO2< 10ppm, hydrogen and nitrogen The molar ratio of gas is 1.5:1；
It 2) is 7000h with air speed by above-mentioned syngas for synthetic ammonia-1In filling ferrum-based catalyst Fe3O4Two concatenated Level-one ammonia synthesis is carried out in one ammonia convertor, the synthesis pressure of the level-one ammonia synthesis is 6MPa, synthesis temperature is 450 DEG C；
3) gaseous mixture come out from first ammonia convertor is with air speed 8000h-1Into two concatenated filling ruthenium bases Second level ammonia synthesis is carried out in second ammonia convertor of catalyst, the synthesis pressure of the second level ammonia synthesis is 5.5MPa, synthesis is warm Degree is 400 DEG C；
Wherein, the ruthenium system ammonia synthesis catalyst by the ruthenium of 4g, the magnesia of 6g, the active carbon of 75g, 8g cerium oxide, The molybdenum oxide of 1.5g, the tungsten oxide of 1g, the barium monoxide of 9g and 3g potassium oxide composition；
The preparation method of above-mentioned ruthenium system ammonia synthesis catalyst, includes the following steps:
(1) basic magnesium carbonate, active carbon, basic carbonate cerium, molybdenum oxide, tungsten oxide, potassium carbonate and barium carbonate ball milling are mixed It closes, collects granularity and be the mixture of 0.2mm, and the mixture is formed, obtain molding；
(2) by the molding incipient impregnation in mass fraction be 9% urea-containing potassium ruthenate aqueous solution in, control The temperature of system dipping is 30 DEG C, and the mass fraction of urea is 8%, after dipping, is taken out；
(3) molding after the dipping is restored in hydrogen, the temperature for controlling reduction is 360 DEG C, and the time is 8h；
(4) molding after the reduction is roasted at 2100 DEG C, obtains ruthenium system ammonia synthesis catalyst.
4) to from second ammonia convertor come out gaseous mixture cool and recycle heat, isolated liquefied ammonia and Remaining gas, and syngas for synthetic ammonia described in the remaining gas and step 1) is mixed.
Comparative example 4
This comparative example provides a kind of ruthenium system ammonia synthesis catalyst and preparation method thereof.The ruthenium system ammonia synthesis catalyst is by 5g Ruthenium, the magnesia of 5g, the cerium oxide of 7g, the molybdenum oxide of 1.5g and 1.5g tungsten oxide composition；
The preparation method of above-mentioned ruthenium system ammonia synthesis catalyst, includes the following steps:
1) by basic magnesium carbonate, basic carbonate cerium, molybdenum oxide and tungsten oxide ball milling mixing, collecting granularity is the mixed of 0.1mm Material is closed, and adds binder-epoxy resin into the mixture and is formed, obtains molding；
2) by the molding incipient impregnation in mass fraction be 12% potassium ruthenate aqueous solution in, control dipping Temperature is 25 DEG C, after dipping, is taken out；
3) molding after the dipping is restored in hydrogen, the temperature for controlling reduction is 350 DEG C, and the time is 9h；
4) molding after the reduction is roasted at 1900 DEG C, obtains ruthenium system ammonia synthesis catalyst.
Comparative example 5
This comparative example provides a kind of ruthenium system ammonia synthesis catalyst and preparation method thereof.The ruthenium system ammonia synthesis catalyst is by 5g Ruthenium, the active carbon of 80g, the cerium oxide of 7g, the molybdenum oxide of 1.5g and 1.5g tungsten oxide composition；
The preparation method of above-mentioned ruthenium system ammonia synthesis catalyst, includes the following steps:
1) by active carbon, basic carbonate cerium, molybdenum oxide and tungsten oxide ball milling mixing, the mixture that granularity is 0.1mm is collected, And add binder-epoxy resin into the mixture and formed, obtain molding；
2) by the molding incipient impregnation in mass fraction be 12% potassium ruthenate aqueous solution in, control dipping Temperature is 25 DEG C, after dipping, is taken out；
3) molding after the dipping is restored in hydrogen, the temperature for controlling reduction is 350 DEG C, and the time is 9h；
4) molding after the reduction is roasted at 1900 DEG C, obtains ruthenium system ammonia synthesis catalyst.
Comparative example 6
This comparative example provides a kind of ruthenium system ammonia synthesis catalyst and preparation method thereof.The ruthenium system ammonia synthesis catalyst is by 8g Ruthenium, the magnesia of 2g, the active carbon of 85g, the cerium oxide of 9g, the molybdenum oxide of 1g, the tungsten oxide of 2g, the barium monoxide of 6g and 6g Potassium oxide composition；
The preparation method of above-mentioned ruthenium system ammonia synthesis catalyst, includes the following steps:
1) by magnesia, active carbon, cerium oxide, molybdenum oxide, tungsten oxide, potassium oxide and barium monoxide ball milling mixing, grain is collected Degree is the mixture of 0.5mm, and forms to the mixture, obtains molding；
2) by the molding incipient impregnation in mass fraction be 15% urea-containing potassium ruthenate aqueous solution in, control The temperature of system dipping is 10 DEG C, and the mass fraction of urea is 5%, after dipping, is taken out；
3) molding after the dipping is restored in hydrogen, the temperature for controlling reduction is 400 DEG C, and the time is 6h；
4) molding after the reduction is dry at 100 DEG C, obtain ruthenium system ammonia synthesis catalyst.
Test example 1
The various embodiments described above and comparative example 1-3 middle outlet ammonia net value, nitrogen utilization rate and hydrogen utilization ratio are surveyed Fixed, corresponding test result is as follows shown in table 1:
Table 1 exports ammonia net value, nitrogen utilization rate and hydrogen utilization ratio
Learn from table 1: ammonia synthesis process is divided into two sections by the present invention, in specified pressure, particular kind of catalyst, specific It is carried out under the unstripped gas of H-N ratio, not only meets ammonia synthesis process requirement, guarantees technique even running, also improve ammonia synthesis Tower exports the utilization rate of ammonia net value and nitrogen and hydrogen.And process operation is steady, low energy consumption.
Test example 2
Ammonia synthesis active testing is carried out to ruthenium system obtained ammonia synthesis catalyst in above-described embodiment 1-7 and comparative example 4-6, Test process is as follows: the ruthenium system ammonia synthesis catalyst of above-mentioned equivalent is loaded on respectively in stainless steel high pressure ammonia convertor, is reacted Gas is hydrogen nitrogen mixed gas, and hydrogen nitrogen volume ratio is 3:1, air speed 10000h-1, reaction pressure 10MPa, reaction temperature 425 ℃.It is corresponding that test result is as follows shown in table 1:
2 ammonia convertor of table is worked off one's feeling vent one's spleen the concentration (V%) of middle ammonia
Learn from table 2: the present invention uses ruthenium, magnesia, active carbon, cerium oxide, molybdenum oxide and tungsten oxide, and limits each group Ratio between point.Reduce carbon content, improve vector stabilisation while, using between each component mutual cooperation, synergistic effect, The Viability reduction of ammino is not resulted in not only, improves that ammino is Viability instead, makes ruthenium system ammonia synthesis catalyst that there is high ammino It is Viability.Specific raw material and maturing temperature are used simultaneously, and the stability and ammino for improving ruthenium system ammonia synthesis catalyst survive Property.
Test example 3
Heat stability testing, phase are carried out to ruthenium system obtained ammonia synthesis catalyst in above-described embodiment 1-7 and comparative example 4-6 The test process answered is as follows: being heated to 1000 DEG C in the case where hydrogen content is 25% atmosphere, and maintains 100h, further takes out, by examination The ammonia synthesis active testing process tested in example 2 is tested, and test result is as follows shown in table 3:
3 ammonia convertor of table is worked off one's feeling vent one's spleen the concentration (V%) of middle ammonia
Learnt from table 3: ruthenium system produced by the present invention ammonia synthesis catalyst above-mentioned high temperature and hydrogeneous atmosphere processing after, then into Row ammonia synthesis active testing, ammonia convertor outlet ammonia density still can reach 24% or more, show its with high heat resistance, and It is not easy methanation, resistance to hydrogen.
Test example 4
Ruthenium system obtained ammonia synthesis in above-described embodiment 1-7 and comparative example 4-6 is tested using Pulse Chemisorption method to be catalyzed The dispersion degree of ruthenium metal in agent, test result is as follows shown in table 4:
The dispersion degree of ruthenium metal in 4 ruthenium system ammonia synthesis catalyst of table
Dispersion degree
Embodiment 1 52%
Embodiment 2 50%
Embodiment 3 50%
Embodiment 4 53%
Embodiment 5 52%
Embodiment 6 55%
Embodiment 7 55%
Comparative example 4 50%
Comparative example 5 50%
Comparative example 6 28%
Learn from table 4: the dispersion degree of ruthenium metal reaches 50% or more in ruthenium system produced by the present invention ammonia synthesis catalyst, table Bright, preparation method of the invention can improve the dispersion degree of ruthenium metal.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments. For those of ordinary skill in the art, other various forms of variations can also be made on the basis of the above description Or it changes.There is no necessity and possibility to exhaust all the enbodiments.And obvious variation extended from this Or it changes still within the protection scope of the invention.

Claims (9)

1. a kind of low pressure ammonia synthesis technology of combined production of methanol, includes the following steps:
1) cryogenic air separation unit is carried out to air, obtains nitrogen and oxygen, the oxygen and natural gas carry out pure oxygen autothermal reforming, obtain Containing CO and H2Gaseous mixture；
2) described it will contain CO and H2Gaseous mixture be divided into two strands, one synthesizing methanol under the effect of the catalyst, another strand of progress electricity Xie Shui separation, obtains hydrogen；
3) be in molar ratio (1.5-2.5) by the hydrogen and nitrogen: 1 is mixed to form syngas for synthetic ammonia, and by the synthesis Ammonia unstripped gas carries out level-one ammonia synthesis, the air speed of the syngas for synthetic ammonia in the first ammonia convertor of filling ferrum-based catalyst For 4000-6000h-1, the synthesis pressure of the level-one ammonia synthesis is 5-7MPa；The synthesis temperature of the level-one ammonia synthesis is 430- 500℃；The ferrum-based catalyst is with mass ratio for (2-3): (1-2): 1 Fe3O4, FeO and K2O is active constituent, with rare earth member Plain oxide and MgAl2O4For auxiliary agent, the content of active constituent is 2-5wt%, rare earth oxide in the ferrum-based catalyst Content is 0.1-0.2wt%, MgAl2O4Content is 0.1-0.2wt%；
4) it is carried out from the second ammonia convertor that the gaseous mixture come out in first ammonia convertor enters filling ruthenium-based catalyst Second level ammonia synthesis, the air speed of the gaseous mixture are 5000-12000h-1, the synthesis pressure of the second level ammonia synthesis is 4-6MPa, institute The synthesis temperature for stating second level ammonia synthesis is 350-435 DEG C；
The ruthenium-based catalyst, the component including following parts by weight: 2-8 parts of ruthenium, 2-8 parts of magnesia, 70-85 parts of active carbon, oxygen Change cerium 3-10 parts, 1-2 parts of molybdenum oxide, 1-2 parts of tungsten oxide.
2. low pressure ammonia synthesis technology according to claim 1, which is characterized in that in step 2), the synthesis temperature of the methanol Degree is 210-250 DEG C, synthesis pressure 5-6MPa；
It further include by described containing CO and H before electrolysis water separation2Gaseous mixture be passed through in waste heat boiler and recycle heat, and High steam is obtained, the step of being pressurized to the syngas for synthetic ammonia is used for.
3. low pressure ammonia synthesis technology according to claim 1 or 2, which is characterized in that the upper half of second ammonia convertor The ruthenium-based catalyst is loaded in part, and the ferrum-based catalyst is loaded in lower half portion, and the syngas for synthetic ammonia is from described first The lower half portion of ammonia convertor enters wherein.
4. low pressure ammonia synthesis technology described in any one of -2 according to claim 1, which is characterized in that first ammonia convertor Number be at least one；
The number of second ammonia convertor is at least one.
5. low pressure ammonia synthesis technology described in any one of -2 according to claim 1, which is characterized in that further include to from described The gaseous mixture come out in two ammonia convertors cools and recycles heat, isolated liquefied ammonia and remaining gas, and by the residue The step of gas and the syngas for synthetic ammonia mix.
6. low pressure ammonia synthesis technology described in any one of -2 according to claim 1, which is characterized in that the active carbon is mixed for nitrogen Miscellaneous active carbon.
7. low pressure ammonia synthesis technology described in any one of -2 according to claim 1, which is characterized in that the ruthenium-based catalyst, Further include the component of following parts by weight:
6-9 parts of barium monoxide
3-9 parts of potassium oxide.
8. low pressure ammonia synthesis technology according to claim 7, which is characterized in that the preparation method of the ruthenium-based catalyst, Include the following steps:
(1) it by basic magnesium carbonate, active carbon, basic carbonate cerium, molybdenum oxide, tungsten oxide, potassium carbonate and barium carbonate ground and mixed, receives Collect mixture, and the mixture is formed, obtains molding；
(2) by the molding be impregnated in ruthenium compound aqueous solution or urea-containing ruthenium compound aqueous solution in, the leaching After stain, take out；
(3) molding after the dipping is restored under reducing atmosphere；
(4) molding after the reduction is roasted at 1600-2500 DEG C, obtains the ruthenium-based ammonia synthetic catalyst.
9. low pressure ammonia synthesis technology described in any one of -2 according to claim 1, which is characterized in that the rare earth element oxidation Object is CeO.
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CN106315619A (en) * 2016-08-18 2017-01-11 福州大学化肥催化剂国家工程研究中心 Low-pressure ammonia synthesis process for in-series iron-based catalysts and ruthenium-based catalysts
CN106513030A (en) * 2016-12-12 2017-03-22 福州大学 Ruthenium-based ammonia synthesis catalyst adopting nitrogen doped activated carbon as carrier and preparation method thereof
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CN106315619A (en) * 2016-08-18 2017-01-11 福州大学化肥催化剂国家工程研究中心 Low-pressure ammonia synthesis process for in-series iron-based catalysts and ruthenium-based catalysts
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