CN103372369A - Method for removing trace impurities from synthesis gas and application of synthesis gas - Google Patents
Method for removing trace impurities from synthesis gas and application of synthesis gas Download PDFInfo
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- CN103372369A CN103372369A CN2012101100135A CN201210110013A CN103372369A CN 103372369 A CN103372369 A CN 103372369A CN 2012101100135 A CN2012101100135 A CN 2012101100135A CN 201210110013 A CN201210110013 A CN 201210110013A CN 103372369 A CN103372369 A CN 103372369A
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Abstract
The invention provides a method for removing trace impurities from a synthesis gas and an application of the synthesis gas. The trace impurities contain carbonyl metal compounds, oxygen, carbonyl sulfur, hydrogen sulfide and hydrogen chloride. The method comprises the step of removing the carbonyl metal compounds, the oxygen, the carbonyl sulfur, the hydrogen sulfide and the hydrogen chloride from the synthesis gas, and a method for removing the carbonyl metal compounds from the synthesis gas comprises the step of enabling the synthesis gas to be in contact with an adsorbent in the presence of oxygen, wherein the contact condition and the concentration of the oxygen ensure that the carbonyl metal compounds adsorbed by the adsorbent are oxidized into metal oxides; and the concentration of the oxygen in mol is 50-500ppm, and the concentration of the carbonyl metal compounds in the synthesis gas in mol is smaller than 10ppm. By adopting the method provided by the invention, the service life of the adsorbent can be prolonged, and the adsorbent has a good adsorption effect, is stable in adsorption and can be used for effectively removing the trace impurities from the synthesis gas.
Description
Technical field
The present invention relates to a kind of method that removes trace impurity in the synthesis gas and process the synthesis gas that obtains through said method as the application of producing at least a raw material in hutanal, isobutylaldehyde, n-butanol, isobutanol and the isooctanol.
Background technology
Synthesis gas is that a kind of main component is CO and H
2Mist, usually also contain lot of trace impurity, for example, except containing micro-ammonia (NH
3), carbonyl iron (Fe (CO)
5, Fe (CO)
4) and carbonyl nickel (Ni (CO)
4) and oxygen (O
2) outside, also contain micro-hydrogen sulfide (H
2S), cos (COS) and hydrogen chloride (HCl).
One of main application of synthesis gas is to carry out hydroformylation reaction with propylene to produce hutanal, isobutylaldehyde, and further hydrogenation obtains n-butanol, isobutanol, and perhaps condensation hydrogenation obtains isooctanol (2-Ethylhexyl Alcohol).The trace impurity O that contains in the forming gas
2Can be with the catalyst ligand triphenylphosphine oxidation of homogeneous catalytic reaction; NH
3, COS, H
2S and HCl can make the rhodium catalyst poisoning of the used costliness of synthetic reaction, active decline; Carbonyl iron and carbonyl nickel can constantly be accumulated after entering carbonyl synthesis reactor, and rhodium catalyst activity expensive in the synthetic reaction is descended, and also cause easily side reaction, thereby cause the reduction of output and the purity of butanols and isooctanol.Therefore, trace impurity prolongs the service life of synthesis reaction catalyst to the impact of the activity and selectivity of subsequent catalyst in the synthesis gas in order to eliminate, and trace impurity in the synthesis gas is down to alap content is necessary.At present, mainly take following methods that described trace impurity is removed.
CN1178766A disclose a kind of utilization through the active fruit shell carbon of overpickling, alkali cleaning as adsorbent, be that 80-150 ℃, air speed are less than 2000h in temperature
-1, pressure is the method that removes carbonyl metal compound in the synthesis gas under the 0.01-20MPa.
CN101224871A discloses a kind of synthesis gas deep-purifying method, and the method comprises synthesis gas successively through adopting the EH-5 hydrolyst with the step of COS hydrolysis, the smart desulfurization of HTS-2 type desulfurizing agent, the dechlorination of ET-3A type protective agent, ET-8A type protective agent decarbonylation Base Metal, the deoxidation of CTO-1 deoxidier, the dearsenification of TAS type Hydrodearsenic Catalyst.After the purification, can reach sulfur content＜10ppb, chlorinity＜10ppb, the content＜20ppb of metal carbonyl, O
2Content＜1ppm, the content＜20ppb of arsenic.
CN101560414A discloses a kind of deep combined purification process for synthetic gas, and synthesis gas successively is converted into organic matter through catalytic hydrogenation the step of inorganic matter, the dearsenification of TAs type Hydrodearsenic Catalyst, the dechlorination of TCl type antichlor, the smart desulfurization of JTS moldeed depth degree desulfurizing agent, ET-8 type protective agent decarbonylation Base Metal, XNOL type olefins hydrogenation deolefination, the deoxidation of TO type deoxidier.After the purification, can reach sulfur content＜10ppb, arsenic content＜10ppb, chlorinity＜10ppb, the content＜20ppb of metal carbonyl, the content＜1ppm of greasy dirt, the content＜0.1ppm of alkene, the content＜1ppm of oxygen.
CN1631530A discloses a kind of PtS
xDehydrogenation catalyst and preparation method thereof.This catalyst is by carrier and the active component platinum sulfide PtS that loads on the carrier
xForm; Wherein, with the weighing scale of carrier, the content of platinum is the 0.01-0.5 % by weight, and the mol ratio x of S/Pt is 0.1-50.At active component PtS
xCatalytic action under, being blended in impurity oxygen in the unstripped gas and hydrogen can water generation reaction, and the oxygen of trace is removed.
The existing method that removes carbonyl metal compound in the synthesis gas mainly adopts the solid absorbents such as active carbon, CuO-ZnO/ active carbon, zeolite and Cu-Zn-Cr oxide with the method for carbonyl metal compound physical absorption at adsorbent surface.But there is the problem of two aspects in the method that adopts physical absorption to remove carbonyl metal compound: the first, and the adsorption capacity of adsorbent is limited, needs often to change adsorbent, two purification adsorption towers perhaps is installed is carried out respectively the sorption and desorption operation; Second, under different temperatures, pressure, there are different physical absorption balances, therefore, along with the change of adsorption tower operating temperature and pressure, desorb may occur in the carbonyl metal compound that is adsorbed on adsorbent surface, thereby the carbonyl metal compound content that purifies in the rear synthesis gas is raise.
In addition, prior art normally adopts and removes first cos (COS), removes the method for oxygen again, and technique is comparatively complicated.
Summary of the invention
The objective of the invention is in order to overcome when adopting existing method to remove carbonyl metal compound in the synthesis gas, exist adsorbent service life short, adsorption effect is poor and adsorb unsettled defective, and is provided a kind of service life that can prolong adsorbent, has the good adsorption effect and adsorbs the stable method that removes trace impurity in the synthesis gas and a kind of application that removes the synthesis gas behind the trace impurity.
The invention provides a kind of method that removes trace impurity in the synthesis gas, described trace impurity contains carbonyl metal compound, oxygen, cos, hydrogen sulfide and hydrogen chloride, the method comprises carbonyl metal compound, oxygen, cos, hydrogen sulfide and hydrogen chloride is removed from described synthesis gas, wherein, the method that removes described carbonyl metal compound is included under the existence of oxygen, described synthesis gas is contacted with adsorbent, and the condition of contact and the concentration of oxygen make the carbonyl metal compound that is adsorbed agent absorption be oxidized to metal oxide; Take the concentration of the described oxygen of mol as 50-500ppm, in the concentration of carbonyl metal compound in the described synthesis gas of mol less than 10ppm.
The present inventor finds, will contact with adsorbent in the concentration of the described carbonyl metal compound of the mol synthesis gas less than 10ppm, and described carbonyl metal compound can be adsorbed by described adsorbent, thereby is enriched in the surface of described adsorbent.What is more important, the condition by control contact and take the concentration of the oxygen of mol under the condition of 50-500ppm, the carbonyl metal compound and the oxygen that are enriched in adsorbent surface are reacted, produce corresponding solid metal oxide.Therefore, adopt method of the present invention not only not exist the problem of carbonyl metal compound parsing, adsorption effect to stablize; Also carbonyl metal compound can be removed from described synthesis gas effectively.In addition, the adsorption area of the solid metal compound of generation on adsorbent is less than corresponding carbonyl metal compound, therefore, can prolong the service life of adsorbent.According to a preferred embodiment of the present invention, with PtS
XCatalyst contacts with the synthesis gas that has removed carbonyl metal compound, not only can make oxygen and hydrogen reaction generate water, can also be hydrogen sulfide with described cos conversion, and through the follow-up step that removes hydrogen sulfide it be removed; Carry out when namely having realized removing oxygen and cos, simplified technique.
In addition, the present invention also provides a kind of synthesis gas that processing obtains through said method as the application of producing at least a raw material in hutanal, isobutylaldehyde, n-butanol, isobutanol and the isooctanol.
Other features and advantages of the present invention will partly be described in detail in the specific embodiment subsequently.
Description of drawings
Fig. 1 is the purified synthesis gas flow chart.
Description of reference numerals:
The 1-water scrubber; The 2-adsorption tower; 3-PtS
X/ A1
2O
3Catalytic tower;
The 4-desulfurizing tower; The 5-dechlorinator.
The specific embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that the specific embodiment described herein only is used for description and interpretation the present invention, is not limited to the present invention.
According to the present invention, the trace impurity in the described synthesis gas contains carbonyl metal compound, oxygen, cos, hydrogen sulfide and hydrogen chloride.As well known to those skilled in the art, impurity in the synthesis gas of separate sources can be different, for example, in the synthesis gas that produces take coal as material gasification, in mol, the concentration of CO is 48 % by mole, the concentration (comprising cos and hydrogen sulfide) of sulphur for the concentration of 3-4.6ppm, hydrogen chloride is that the concentration of 0.3-0.88ppm, carbonyl metal compound is that the concentration of 0.5-0.98ppm, oxygen is 1-8ppm, and all the other are H
2
Need to prove that ppm of the present invention and ppb all are in mol.For example, the concentration of sulphur is that 3-4.6ppm represents that the concentration of sulphur described in 1,000,000 moles the synthesis gas is 3-4.6mol.
According to the present invention, the described method of trace impurity that removes in the synthesis gas comprises carbonyl metal compound, oxygen, cos, hydrogen sulfide and hydrogen chloride is removed from described synthesis gas, wherein, the method that removes described carbonyl metal compound is included under the existence of oxygen, described synthesis gas is contacted with adsorbent, and the condition of contact and the concentration of oxygen make the carbonyl metal compound that is adsorbed agent absorption be oxidized to metal oxide; The concentration of described oxygen is 50-500ppm, is preferably 50-250ppm; The concentration of carbonyl metal compound is preferably 5ppb-5ppm less than 10ppm in the described synthesis gas.
The mechanism that removes described carbonyl metal compound of the present invention may be as follows:
(1) physical absorption: Fe (CO)
5+ AC → Fe (CO)
5/ AC
Fe(CO)
4+AC→Fe(CO)
4/AC
Ni(CO)
4+AC→Ni(CO)
4/AC
(2) oxidation reaction: Fe (CO)
5/ AC+O
2→ Fe
2O
3/ AC
Fe(CO)
4/AC+O
2→Fe
2O
3/AC
Ni(CO)
4/AC+O
2→NiO/AC
Wherein, AC represents adsorbent.
Need to prove, of the present inventionly remove that the method for carbonyl metal compound is specially adapted to the concentration of described carbonyl metal compound less than the synthesis gas of 10ppm in the synthesis gas, more be specially adapted to the concentration of described carbonyl metal compound less than the synthesis gas of 5ppm.For the concentration of the carbonyl metal compound synthesis gas greater than 10ppm, should adopt first additive method that the concentration of carbonyl metal compound is down to less than adopting method of the present invention to carry out deep purifying behind the 10ppm again.
According to the present invention, itself contain a small amount of trace impurity oxygen in the described synthesis gas, when the concentration of the oxygen that itself contains in the synthesis gas during less than 50ppm, need the outer oxygen that adds take the total concentration of the oxygen that guarantees oxygen that synthesis gas itself contains and outer adding as 50-500ppm; When itself oxygen concentration in the synthesis gas during greater than 50ppm, then do not need outer adding oxygen.When the total content of oxygen during greater than 50ppm, just carbonyl metal compound can be removed effectively, and excessive oxygen is helpless to the significant decline of carbonyl metal compound content, on the contrary, also can increase the load of follow-up deoxidation tower.
According to the present invention, the volume space velocity when condition of described contact comprises the gas of the pressure of temperature, contact of contact and synthesis gas, wherein, can be adsorbed agent absorption as long as the condition of described contact can satisfy described carbonyl metal compound, and in the presence of oxygen, be converted into corresponding metal oxide and get final product.Under the preferable case, the temperature of described contact can be 50-250 ℃, and the pressure of described contact can be 0.1-10MPa, and volume space velocity is 500-6000h during the gas of described synthesis gas
-1More preferably in the situation, the temperature of described contact is 50-150 ℃, and the pressure of described contact is 0.1-5MPa, and volume space velocity is 800-3000h during the gas of described synthesis gas
-1
Wherein, the definition of volume space velocity was a kind of representation of air speed when volume space velocity was the conventional gas that uses in this area during described gas, referred to the volume of the described synthesis gas of the adsorbent that per hour passes through unit volume.
According to the present invention, described adsorbent can be the existing various adsorbents that can adsorb described carbonyl metal compound, and for example, described adsorbent can be active carbon.As everyone knows, described active carbon is a kind of porous carbonaceous material, its highly developed pore structure makes it have huge surface area, thus be easy to synthesis gas in carbonyl metal compound fully contact, thereby give active carbon peculiar absorption property.For the specific area that further increases described adsorbent, improve its adsorption capacity, under the preferable case, described adsorbent can also be for comprising carrier and loading on the adsorbent of the active component on the described carrier; And take the gross mass of described adsorbent as benchmark, the content of described active component can be the 10-50 % by weight, and the content of described carrier can be the 50-90 % by weight.
According to the present invention, described active component can be the existing various active component that can adsorb described carbonyl metal compound, described carrier also can be existing various carrier that can load active component, for example, described active component can be the mixture of cupric oxide and zinc oxide, and described carrier can be active carbon.Under the preferable case, take the gross mass of described adsorbent as benchmark, the content of described cupric oxide is the 3-20 % by weight, and the content of described zinc oxide is the 10-30 % by weight, and the content of described active carbon is the 60-85 % by weight.
The present invention is not particularly limited the BET specific area of described active carbon, but those skilled in the art can be understood that easily, the BET specific area that increases described active carbon is conducive to the raising of described carbonyl metal compound adsorption efficiency, therefore, preferably, the BET specific area of described active carbon is greater than 600m
2/ g, more preferably 800-1500m
2/ g, more preferably 1000-1500m
2/ g.The bulk density of described active carbon can change in a big way, is not particularly limited, and for example, described bulk density can be 0.3-0.65g/cm
3, be preferably 0.3-0.45g/cm
3
The present invention is not particularly limited the raw material for preparing described active carbon, and for example, described active carbon can be selected from the active carbon for preparing with one or more raw materials in shell, wood chip and the anthracite.But, the BET specific area of the active carbon that different material prepares there are differences, wherein, the specific area of the active carbon for preparing take shell as raw material is maximum, intensity is higher, adsorption capacity is the strongest, therefore, in order to improve the adsorption efficiency of described adsorbent, under the preferable case, the active carbon of described active carbon for preparing take shell as raw material, the active carbon that more preferably prepares take coconut husk as raw material.
According to the present invention, the method that removes described oxygen and cos can be the existing various methods that remove oxygen and cos, for example, the synthesis gas that has removed carbonyl metal compound can be contacted with the CTO-1 deoxidier carry out deoxidation after, contact with HTS-2 type desulfurizing agent again and carry out smart desulfurization; Wherein, described CTO-1 deoxidier is the deoxidier that is comprised of cerium oxide, cupric oxide, molybdenum trioxide and alumina support; Described HTS-2 type desulfurizing agent is by cupric oxide and iron monoxide composite oxides, or the desulfurizing agent of zinc oxide and copper monoxide composite oxides composition.But in order to simplify working process, under the preferable case, to remove oxygen and cos and carry out simultaneously.Method with oxygen and carbonyl sulfide removal comprises and will remove synthesis gas and the PtS of carbonyl metal compound simultaneously
XThe catalyst contact, the condition of contact is so that described oxygen conversion is water, and described cos conversion is hydrogen sulfide.In addition, PtS
XCatalyst has the ability of very strong anti-sulfur poisoning, therefore, can also prolong the service life of described catalyst.
According to the present invention, described PtS
XCatalyst comprises carrier and the active component platinum sulfide PtS that loads on the carrier
X, wherein, take the gross weight of carrier as benchmark, the content of described platinum is the 0.075-0.085 % by weight, S/Pt mol ratio x is 10-20, and described carrier can be selected from any one in alundum (Al2O3), molecular sieve, silica and the active carbon, is preferably alundum (Al2O3).Described PtS
XCatalyst can be commercially available, and also can prepare according to CN1631530A or the disclosed method of CN1768936A.
The present invention is to described synthesis gas and the PtS that has removed carbonyl metal compound
XThe condition of catalyst contact is not particularly limited, as long as oxygen can be removed and be hydrogen sulfide with described cos conversion, as a rule, the volume space velocity when condition of described contact comprises the gas of the pressure of the temperature of contact, contact and synthesis gas.The temperature of described contact for example can be 150-200 ℃, and the pressure of contact can be 2-5MPa, and volume space velocity can be 1000-2000h during the gas of synthesis gas
-1Under the preferable case, the temperature of described contact is 180-190 ℃, and the pressure of contact is 2-2.5MPa, and volume space velocity is 1000-1800h during the gas of synthesis gas
-1
According to the present invention, the method that removes described hydrogen sulfide can contact with desulfurizing agent for the synthesis gas that will remove carbonyl metal compound, oxygen and cos usually.The most frequently used active component of described desulfurizing agent is zinc oxide, and described zinc oxide can generate zinc sulphide with the hydrogen sulfide reaction, thereby described hydrogen sulfide is removed from synthesis gas.Described desulfurizing agent can be commercially available, for example, and the T306 desulfurizing agent that can produce available from the Kunshan City Precise chemical engineering Research Institute Co., Ltd, the KATALCO 32-4 desulfurizing agent that also can produce available from Johnson Matthey company etc.The temperature that the condition that synthesis gas is contacted with desulfurizing agent generally includes contact can be 150-200 ℃, and the pressure of contact can be 2-5MPa, and volume space velocity can be 1000-2000h during the gas of synthesis gas
-1Under the preferable case, the temperature of described contact is 180-190 ℃, and the pressure of contact is 2-2.5MPa, and volume space velocity is 1500-2000h during the gas of synthesis gas
-1
The present invention is not particularly limited the method that removes described hydrogen chloride, for example, can contact with antichlor for the synthesis gas that will remove carbonyl metal compound, oxygen, cos and hydrogen sulfide.As a rule, described desulfurizing agent comprises carrier and the active component that loads on the carrier; Take the gross mass of described desulfurizing agent as benchmark, the content of described carrier can be the 50-90 % by weight; The content of described active component can be the 10-50 % by weight.Described active component is preferably sodium oxide molybdena; Described carrier can be various carriers that can the described active component of load, for example, can be in alundum (Al2O3), molecular sieve, silica and the active carbon any one, is preferably alundum (Al2O3).Described antichlor can be commercially available, for example, and the T402 antichlor that can produce available from the Kunshan City Precise chemical engineering Research Institute Co., Ltd, the KATALCO 59-3 antichlor that also can produce available from Johnson Matthey company etc.The temperature that the condition that synthesis gas is contacted with antichlor generally includes contact can be 150-200 ℃, and the pressure of contact can be 2-5MPa, and volume space velocity can be 1000-2000h during the gas of synthesis gas
-1Under the preferable case, the temperature of described contact is 180-190 ℃, and the pressure of contact is 2-2.5MPa, and volume space velocity is 1500-2000h during the gas of synthesis gas
-1
Need to prove that the order that removes described hydrogen sulfide and hydrogen chloride also can be exchanged, and can't affect the effect that removes hydrogen sulfide and hydrogen chloride.That is, can first the synthesis gas that has removed carbonyl metal compound, oxygen and cos be contacted to remove hydrogen sulfide with desulfurizing agent, the synthesis gas that will remove again hydrogen sulfide contacts to remove hydrogen chloride with antichlor; Also can first the synthesis gas that has removed carbonyl metal compound, oxygen and cos be contacted to remove hydrogen chloride with antichlor, will remove again the synthesis gas behind the hydrogen chloride and contact to remove hydrogen sulfide with desulfurizing agent.
According to the present invention, when described trace impurity also contained ammonia, method of the present invention also was included in and removes before the described carbonyl metal compound, and described ammonia is removed.Ammonia is very easily water-soluble, can generate a hydration ammonia (NH by Hydrogenbond with hydrone
3H
2O).Therefore, in order to remove the ammonia in the synthesis gas, before removing described carbonyl metal compound, described synthesis gas can be contacted with water.The condition of described contact is as well known to those skilled in the art, and for example, the condition of described contact can comprise that the mol ratio of synthesis gas and water is 2-4: 1, and the temperature of contact is 20-50 ℃, the pressure of contact is 2-5MPa; Under the preferable case, the mol ratio of described synthesis gas and water is 2-2.5: 1, and the temperature of contact is 30-40 ℃, the pressure of contact is 2-2.5MPa.
Below in conjunction with the description of drawings method that removes trace impurity in the synthesis gas provided by the invention.
As shown in Figure 1, provided by the inventionly remove the method for trace impurity in the synthesis gas and comprise that the synthesis gas that will contain ammonia, carbonyl metal compound, oxygen, cos, hydrogen sulfide and hydrogen chloride is successively by water scrubber 1, adsorption tower 2, PtS
X/ Al
2O
3Catalytic tower 3, desulfurizing tower 4 and dechlorinator 5.Wherein, in the described water scrubber 1 water is housed; Be filled with in the adsorption tower 2 can the adsorption of metal carbonyls compound adsorbent, described adsorbent is active carbon, perhaps described adsorbent can be for comprising absorbent charcoal carrier and loading on active component cupric oxide on the described absorbent charcoal carrier and the adsorbent of zinc oxide; Be filled with desulfurizing agent in the described desulfurizing tower 4; Be filled with antichlor among the described dechlorinator 5.
The bottom of pending synthesis gas from water scrubber 1 passed into the water scrubber 1, water elution except the synthesis gas of the ammonia Base top contact from water scrubber 1, and is passed into the described adsorption tower 2 from the top of adsorption tower 2; One oxygen intake is arranged at the top of described adsorption tower 2, if the concentration of the oxygen from the synthesis gas of the Base top contact of described water scrubber 1 is less than 50ppm, then can pass into an amount of oxygen to enter the synthesis gas self of described adsorption tower 2 oxygen that contains and the oxygen concentration sum that adds be 50-500ppm by this oxygen intake; If the concentration of the oxygen from the synthesis gas of the Base top contact of described water scrubber 1 is then closed this oxygen intake greater than 50ppm; Content by control contact conditions and oxygen is oxidized to corresponding metal oxide with the carbonyl metal compound that will remove in the synthesis gas behind the ammonia, and the synthesis gas after carbonyl metal compound is removed is drawn from the bottom of adsorption tower 2, and from PtS
X/ Al
2O
3Described PtS is introduced at the top of catalytic tower 3
X/ Al
2O
3Catalytic tower 3 take oxygen is removed and with cos conversion as hydrogen sulfide; To remove oxygen and be that synthesis gas behind the hydrogen sulfide is from PtS with cos conversion
X/ Al
2O
3Draw the bottom of catalytic tower 3, and introduce described desulfurizing tower 4 from the top of desulfurizing tower 4 with hydrogen sulfide stripping; The synthesis gas that removes behind the hydrogen sulfide is drawn from the bottom of desulfurizing tower 4, and introduce from dechlorinator 5 top the described dechlorinator 5 that hydrogen chloride is removed, the synthesis gas that removes behind the hydrogen chloride is drawn from described dechlorinator's 5 bottom.
In addition, the present invention also provides the application of a kind of synthesis gas as the raw material of producing hutanal, isobutylaldehyde, n-butanol, isobutanol and isooctanol, wherein, and the synthesis gas of described synthesis gas for preparing as stated above.The method for preparing hutanal, isobutylaldehyde, n-butanol, isobutanol and isooctanol (2-Ethylhexyl Alcohol) is as well known to those skilled in the art, here gives unnecessary details no longer one by one.
Described in embodiment and the Comparative Examples in the synthesis gas concentration of ammonia measure (UV-3600 of Shimadzu company ultraviolet-uisible spectrophotometer) by clorox-salicylic acid spectrophotometric analysis; The concentration of carbonyl metal compound is measured by the 7500CX inductivity coupled plasma mass spectrometry (ICP-MS) of Agilent company; The concentration of described oxygen adopts DF-310 and the DF-560 trace oxygen analyzer of Delta F company to measure; The concentration of described sulphur adopts the 200SA Sulfur Analysis instrument of Ge Maike instrument company to measure; The concentration of described hydrogen chloride adopts the mercuric thiocyanate colorimetric method to measure (UV-3600 of Shimadzu company ultraviolet-uisible spectrophotometer).
This embodiment is used for illustrating the method that removes the synthesis gas trace impurity of the present invention.
By purified synthesis gas flow chart shown in Figure 1 described synthesis gas is processed, wherein, the flow of washings is 1.674mol/h in the water scrubber 1, and the BET specific area that is filled with 50mL in the adsorption tower 2 is 1250m
2/ g, bulk density are 0.38g/cm
3Cocoanut active charcoal; PtS
X/ Al
2O
3Be filled with the PtS of 75mL in the catalytic tower 3
X/ Al
2O
3Catalyst is (wherein, with Al
2O
3The gross weight of carrier is benchmark, and the content of described platinum is 0.085 % by weight, and S/Pt mol ratio x is 15); Be filled with the T306 desulfurizing agent available from Kunshan City Precise chemical engineering Research Institute Co., Ltd production of 50mL in the desulfurizing tower 4; Be filled with the T402 antichlor of the Kunshan City Precise chemical engineering Research Institute Co., Ltd production of 50mL among the dechlorinator 5.
With pending synthesis gas (wherein, n (H
2): the concentration of n (CO)=1: 1, sulphur is that the concentration of 4.6ppm, ammonia is that the concentration of 8.8ppm, hydrogen chloride is that the concentration of 0.88ppm, carbonyl iron is that the concentration of 2ppm (take Fe), carbonyl nickel is 1ppm as the concentration of 1.8ppm (take Ni), oxygen) pass into the water scrubber 1 from the bottom of water scrubber 1, and the mol ratio of control synthesis gas and water is 2, temperature is that 30 ℃, pressure are that 2.0MPa is to remove the ammonia in the described synthesis gas; With water elution except the Base top contact of the synthesis gas behind the ammonia from water scrubber 1, and introduce the described adsorption tower 2 from the top of adsorption tower 2, open simultaneously that the oxygen intake that is positioned at described adsorption tower 2 tops passes into an amount of oxygen to enter the oxygen that the synthesis gas self of described adsorption tower 2 contains be 150ppm with the oxygen concentration sum that adds, and the control temperature be 90 ℃, pressure when being the gas of 2.0MPa, synthesis gas volume space velocity be 1500h
-1So that the carbonyl metal compound in the synthesis gas is oxidized to corresponding metal oxide; The synthesis gas that removes behind the carbonyl metal compound is drawn from the bottom of adsorption tower 2, and from PtS
X/ Al
2O
3Described PtS is introduced at the top of catalytic tower 3
X/ Al
2O
3Catalytic tower 3, and the control temperature be 180 ℃, pressure when being the gas of 2.0MPa, synthesis gas volume space velocity be 1000h
-1Take the oxygen in the synthesis gas is removed and with cos conversion as hydrogen sulfide; To remove oxygen and be that synthesis gas behind the hydrogen sulfide is from PtS with cos conversion
X/ Al
2O
3Draw the bottom of catalytic tower 3, introduces described desulfurizing tower 4 from the top of desulfurizing tower 4, and the control temperature be 180 ℃, pressure when being the gas of 2.0MPa, synthesis gas volume space velocity be 1500h
-1With with the hydrogen sulfide stripping in the synthesis gas; The synthesis gas that removes behind the hydrogen sulfide is drawn from the bottom of desulfurizing tower 4, introduces the described dechlorinator 5 from dechlorinator 5 top, and the control temperature be 180 ℃, pressure when being the gas of 2.0MPa, synthesis gas volume space velocity be 1500h
-1So that the hydrogen chloride in the synthesis gas is removed, the synthesis gas that removes behind the hydrogen chloride is drawn from described dechlorinator's 5 bottom.
Within two weeks of cleaning test, adopting in the synthesis gas after above-mentioned condition purifies, the concentration of sulphur is always≤concentration of 5ppb, ammonia is always≤concentration of 0.05ppm, hydrogen chloride is always≤concentration of 0.01ppm, carbonyl metal compound is always≤and the concentration of 4.8ppb (in Fe, Ni), oxygen is always≤0.01ppm.
This embodiment is used for illustrating the method that removes the synthesis gas trace impurity of the present invention.
Method according to embodiment 1 removes the trace impurity in the synthesis gas, and different is, the amount that oxygen passes into is to enter the synthesis gas self of described adsorption tower 2 oxygen that contains and the oxygen concentration sum that adds be 50ppm.Within two weeks of cleaning test, adopting in the synthesis gas after above-mentioned condition purifies, the concentration of sulphur is always≤concentration of 5ppb, ammonia is always≤concentration of 0.05ppm, hydrogen chloride is always≤concentration of 0.01ppm, carbonyl metal compound is always≤and the concentration of 5ppb (in Fe, Ni), oxygen is always≤0.006ppm.
Embodiment 3
This embodiment is used for illustrating the method that removes the synthesis gas trace impurity of the present invention.
Method according to embodiment 1 removes the trace impurity in the synthesis gas, and different is, the amount that oxygen passes into is to enter the synthesis gas self of described adsorption tower 2 oxygen that contains and the oxygen concentration sum that adds be 350ppm.Within two weeks of cleaning test, adopting in the synthesis gas after above-mentioned condition purifies, the concentration of sulphur is always≤concentration of 5ppb, ammonia is always≤concentration of 0.05ppm, hydrogen chloride is always≤concentration of 0.01ppm, carbonyl metal compound is always≤and the concentration of 4.5ppb (in Fe, Ni), oxygen is always≤0.1ppm.
Embodiment 4
This embodiment is used for illustrating the method that removes the synthesis gas trace impurity of the present invention.
Method according to embodiment 1 removes the trace impurity in the synthesis gas, and different is n (H in the described synthesis gas
2): n (CO)=1: 3.Within two weeks of cleaning test, adopting in the synthesis gas after above-mentioned condition purifies, the concentration of sulphur is always≤concentration of 5ppb, ammonia is always≤concentration of 0.05ppm, hydrogen chloride is always≤concentration of 0.01ppm, carbonyl metal compound is always≤and the concentration of 4.9ppb (in Fe, Ni), oxygen is always≤0.01ppm.
Embodiment 5
This embodiment is used for illustrating the method that removes the synthesis gas trace impurity of the present invention.
Method according to embodiment 1 removes the trace impurity in the synthesis gas, and different is that the temperature when removing carbonyl metal compound is 150 ℃.Within two weeks of cleaning test, adopting in the synthesis gas after above-mentioned condition purifies, the concentration of sulphur is always≤concentration of 5ppb, ammonia is always≤concentration of 0.05ppm, hydrogen chloride is always≤concentration of 0.01ppm, carbonyl metal compound is always≤and the concentration of 4.2ppb (in Fe, Ni), oxygen is always≤0.01ppm.
Embodiment 6
This embodiment is used for illustrating the method that removes the synthesis gas trace impurity of the present invention.
Method according to embodiment 1 removes the trace impurity in the synthesis gas, and different is that the temperature when removing carbonyl metal compound is 180 ℃.Within two weeks of cleaning test, adopting in the synthesis gas after above-mentioned condition purifies, the concentration of sulphur is always≤concentration of 5ppb, ammonia is always≤concentration of 0.05ppm, hydrogen chloride is always≤concentration of 0.01ppm, carbonyl metal compound is always≤and the concentration of 3.5ppb (in Fe, Ni), oxygen is always≤0.01ppm.
Embodiment 7
This embodiment is used for illustrating the method that removes the synthesis gas trace impurity of the present invention.
Method according to embodiment 1 removes the trace impurity in the synthesis gas, and different is that the pressure when removing carbonyl metal compound is 1MPa.Within two weeks of cleaning test, adopting in the synthesis gas after above-mentioned condition purifies, the concentration of sulphur is always≤concentration of 5ppb, ammonia is always≤concentration of 0.05ppm, hydrogen chloride is always≤concentration of 0.01ppm, carbonyl metal compound is always≤and the concentration of 5.8ppb (in Fe, Ni), oxygen is always≤0.01ppm.
Embodiment 8
This embodiment is used for illustrating the method that removes the synthesis gas trace impurity of the present invention.
Method according to embodiment 1 removes the trace impurity in the synthesis gas, and different is that the pressure when removing carbonyl metal compound is 3MPa.Within two weeks of cleaning test, adopting in the synthesis gas after above-mentioned condition purifies, the concentration of sulphur is always≤concentration of 5ppb, ammonia is always≤concentration of 0.05ppm, hydrogen chloride is always≤concentration of 0.01ppm, carbonyl metal compound is always≤and the concentration of 3.9ppb (in Fe, Ni), oxygen is always≤0.01ppm.
Embodiment 9
This embodiment is used for illustrating the method that removes the synthesis gas trace impurity of the present invention.
Method according to embodiment 1 removes the trace impurity in the synthesis gas, and different is, the loadings by changing the adsorbent in the adsorption tower 2 is so that volume space velocity is 1000h during the gas when removing carbonyl metal compound
-1Within two weeks of cleaning test, adopting in the synthesis gas after above-mentioned condition purifies, the concentration of sulphur is always≤concentration of 5ppb, ammonia is always≤concentration of 0.05ppm, hydrogen chloride is always≤concentration of 0.01ppm, carbonyl metal compound is always≤and the concentration of 4.5ppb (in Fe, Ni), oxygen is always≤0.01ppm.
Embodiment 10
This embodiment is used for illustrating the method that removes the synthesis gas trace impurity of the present invention.
Method according to embodiment 1 removes the trace impurity in the synthesis gas, and different is, the loadings by changing the adsorbent in the adsorption tower 2 is so that volume space velocity is 3000h during the gas when removing carbonyl metal compound
-1Within two weeks of cleaning test, adopting in the synthesis gas after above-mentioned condition purifies, the concentration of sulphur is always≤concentration of 5ppb, ammonia is always≤concentration of 0.05ppm, hydrogen chloride is always≤concentration of 0.01ppm, carbonyl metal compound is always≤and the concentration of 6.5ppb (in Fe, Ni), oxygen is always≤0.01ppm.
Embodiment 11
This embodiment is used for illustrating the method that removes the synthesis gas trace impurity of the present invention.
Method according to embodiment 1 removes the trace impurity in the synthesis gas, and different is that the BET specific surface of used cocoanut active charcoal is 850m when removing carbonyl metal compound
2/ g, bulk density is 0.42g/cm
3Within two weeks of cleaning test, adopting in the synthesis gas after above-mentioned condition purifies, the concentration of sulphur is always≤concentration of 5ppb, ammonia is always≤concentration of 0.05ppm, hydrogen chloride is always≤concentration of 0.01ppm, carbonyl metal compound is always≤and the concentration of 7.6ppb (in Fe, Ni), oxygen is always≤0.01ppm.
Embodiment 12
This embodiment is used for illustrating the method that removes the synthesis gas trace impurity of the present invention.
Method according to embodiment 11 removes the trace impurity in the synthesis gas, and different is when removing carbonyl metal compound, to replace cocoanut active charcoal with coal mass active carbon.Within two weeks of cleaning test, adopting in the synthesis gas after above-mentioned condition purifies, the concentration of sulphur is always≤concentration of 5ppb, ammonia is always≤concentration of 0.05ppm, hydrogen chloride is always≤concentration of 0.01ppm, carbonyl metal compound is always≤and the concentration of 8.9ppb (in Fe, Ni), oxygen is always≤0.01ppm.
Embodiment 13
This embodiment is used for illustrating the method that removes the synthesis gas trace impurity of the present invention.
Method according to embodiment 1 removes the trace impurity in the synthesis gas, and different is that the concentration that removes carbonyl metal compound in the described synthesis gas is 9ppm.Within two weeks of cleaning test, adopting in the synthesis gas after above-mentioned condition purifies, the concentration of sulphur is always≤concentration of 5ppb, ammonia is always≤concentration of 0.05ppm, hydrogen chloride is always≤concentration of 0.01ppm, carbonyl metal compound is always≤and the concentration of 7.5ppb (in Fe, Ni), oxygen is always≤0.01ppm.
Embodiment 14
This embodiment is used for illustrating the method that removes the synthesis gas trace impurity of the present invention.
Method according to embodiment 1 removes the trace impurity in the synthesis gas, different is, when removing carbonyl metal compound, described adsorbent is to comprise absorbent charcoal carrier and load on cupric oxide on the absorbent charcoal carrier and the adsorbent of zinc oxide, wherein, take the gross mass of described adsorbent as benchmark, the content of described cupric oxide is 10 % by weight, the content of described zinc oxide is 20 % by weight, and the content of described active carbon is 70 % by weight.Within two weeks of cleaning test, adopting in the synthesis gas after above-mentioned condition purifies, the concentration of sulphur is always≤concentration of 5ppb, ammonia is always≤concentration of 0.05ppm, hydrogen chloride is always≤concentration of 0.01ppm, carbonyl metal compound is always≤and the concentration of 6.8ppb (in Fe, Ni), oxygen is always≤0.01ppm.
Embodiment 15
This embodiment is used for illustrating the method that removes the synthesis gas trace impurity of the present invention.
By purified synthesis gas flow chart shown in Figure 1 described synthesis gas is processed, wherein, the flow of washings is 341.5Kmol/h in the water scrubber 1, is filled with 8.5m in the adsorption tower 2
3The BET specific area be 1150m
2/ g, bulk density are 0.42g/cm
3Cocoanut active charcoal; PtS
X/ Al
2O
3Be filled with 8.5m in the catalytic tower 3
3PtS
X/ Al
2O
3Catalyst is (wherein, with Al
2O
3The gross weight of carrier is benchmark, and the content of described platinum is 0.085 % by weight, and S/Pt mol ratio x is 15); Be filled with 10.2m in the desulfurizing tower 4
3The T306 desulfurizing agent of producing available from the Kunshan City Precise chemical engineering Research Institute Co., Ltd; Be filled with 10.2m among the dechlorinator 5
3The T402 antichlor produced of Kunshan City Precise chemical engineering Research Institute Co., Ltd.
With pending synthesis gas (wherein, n (H
2): the concentration of n (CO)=1: 1, sulphur is that the concentration of 4.6ppm, ammonia is that the concentration of 8.8ppm, hydrogen chloride is that the concentration of 0.88ppm, carbonyl iron is that the concentration of 2ppm (take Fe), carbonyl nickel is 1ppm as the concentration of 1.8ppm (take Ni), oxygen) pass into the water scrubber 1 from the bottom of water scrubber 1, and the mol ratio of control synthesis gas and water is 2, temperature is that 30 ℃, pressure are that 2.4MPa is to remove the ammonia in the described synthesis gas; With water elution except the Base top contact of the synthesis gas behind the ammonia from water scrubber 1, and introduce the described adsorption tower 2 from the top of adsorption tower 2, open simultaneously that the oxygen intake that is positioned at described adsorption tower 2 tops passes into an amount of oxygen to enter the oxygen that the synthesis gas self of described adsorption tower 2 contains be 150ppm with the oxygen concentration sum that adds, and the control temperature be 80 ℃, pressure when being the gas of 2.4MPa, synthesis gas volume space velocity be 1800h
-1So that the carbonyl metal compound in the synthesis gas is oxidized to corresponding metal oxide; The synthesis gas that removes behind the carbonyl metal compound is drawn from the bottom of adsorption tower 2, and from PtS
X/ Al
2O
3Described PtS is introduced at the top of catalytic tower 3
X/ Al
2O
3Catalytic tower 3, and the control temperature be 190 ℃, pressure when being the gas of 2.4MPa, synthesis gas volume space velocity be 1800h
-1Take the oxygen in the synthesis gas is removed and with cos conversion as hydrogen sulfide; To remove oxygen and be that synthesis gas behind the hydrogen sulfide is from PtS with cos conversion
X/ Al
2O
3Draw the bottom of catalytic tower 3, introduces described desulfurizing tower 4 from the top of desulfurizing tower 4, and the control temperature be 180 ℃, pressure when being the gas of 2.4MPa, synthesis gas volume space velocity be 1500h
-1With with the hydrogen sulfide stripping in the synthesis gas; The synthesis gas that removes behind the hydrogen sulfide is drawn from the bottom of desulfurizing tower 4, introduces the described dechlorinator 5 from dechlorinator 5 top, and the control temperature be 180 ℃, pressure when being the gas of 2.4MPa, synthesis gas volume space velocity be 1500h
-1So that the hydrogen chloride in the synthesis gas is removed, the synthesis gas that removes hydrogen chloride is drawn from described dechlorinator's 5 bottom and send into the synthesis reactor as the raw material of producing hutanal, isobutylaldehyde, n-butanol, isobutanol and isooctanol.
In the commerical test in 3 years, adopt in the synthesis gas after above-mentioned condition purifies, the concentration of sulphur all the time less than the concentration of 6ppb, ammonia all the time less than the concentration of 0.05ppm, hydrogen chloride all the time less than the concentration of 0.01ppm, carbonyl metal compound all the time less than the concentration of 5ppb (in Fe, Ni), oxygen all the time less than 0.01ppm.
Embodiment 16
This embodiment is used for illustrating the method that removes the synthesis gas trace impurity of the present invention.
Method according to embodiment 15 removes the trace impurity in the synthesis gas, and different is, uses after 2 years, stops to add oxygen in adsorption tower, and the concentration of carbonyl metal compound progressively rises to 1ppm (in Fe, Ni) in the synthesis gas after then purifying.Recover oxygenation so that enter after the synthesis gas self of described adsorption tower 2 oxygen that contains and the oxygen concentration sum that adds be 150ppm, the concentration of carbonyl metal compound is down to less than 5ppb (in Fe, Ni) in the decontaminating syngas.
Embodiment 17
This embodiment is used for illustrating the method that removes the synthesis gas trace impurity of the present invention.
Method according to embodiment 15 removes the trace impurity in the synthesis gas, different is, use after 2 years, stop oxygen and reaction temperature is brought up to 90 ℃, the concentration of carbonyl metal compound progressively rises to 1.8ppm (in Fe, Ni) in the synthesis gas after then purifying.Recover oxygenation so that enter after the synthesis gas self of described adsorption tower 2 oxygen that contains and the oxygen concentration sum that adds be 150ppm, the concentration of carbonyl metal compound is down to less than 5ppb (in Fe, Ni) in the decontaminating syngas.
Comparative Examples 1
This embodiment is used for the method that removes the synthesis gas trace impurity of explanation reference.
Method according to embodiment 1 removes the trace impurity in the synthesis gas, and different is, when removing carbonyl metal compound, does not pass into oxygen in the synthesis gas that enters described adsorption tower 2, that is, the concentration of oxygen is 1ppm.Within two weeks of cleaning test, adopting in the synthesis gas after above-mentioned condition purifies, the concentration of sulphur is always≤concentration of 5ppb, ammonia is always≤concentration of 0.05ppm, hydrogen chloride is always≤concentration of 0.01ppm, carbonyl metal compound is always≤and the concentration of 35ppb (in Fe, Ni), oxygen is always≤0.01ppm.
Comparative Examples 2
This Comparative Examples is used for the method that removes the synthesis gas trace impurity of explanation reference.
Method according to embodiment 1 removes the trace impurity in the synthesis gas, and different is, the amount that oxygen passes into is to enter the synthesis gas self of described adsorption tower 2 oxygen that contains and the oxygen concentration sum that adds be 25ppm.Within two weeks of cleaning test, adopting in the synthesis gas after above-mentioned condition purifies, the concentration of sulphur is always≤concentration of 5ppb, ammonia is always≤concentration of 0.05ppm, hydrogen chloride is always≤concentration of 0.01ppm, carbonyl metal compound is always≤and the concentration of 10.8ppb (in Fe, Ni), oxygen is always≤0.005ppm.
Comparative Examples 3
This embodiment is used for the method that removes the synthesis gas trace impurity of explanation reference.
Method according to embodiment 12 removes the trace impurity in the synthesis gas, and different is, when removing carbonyl metal compound, does not pass into oxygen in the synthesis gas that enters described adsorption tower 2, that is, the concentration of oxygen is 1ppm.Within two weeks of cleaning test, adopting in the synthesis gas after above-mentioned condition purifies, the concentration of sulphur is always≤concentration of 5ppb, ammonia is always≤concentration of 0.05ppm, hydrogen chloride is always≤concentration of 0.01ppm, carbonyl metal compound is always≤and the concentration of 45ppb (in Fe, Ni), oxygen is always≤0.01ppm.
Comparative Examples 4
This embodiment is used for the method that removes the synthesis gas trace impurity of explanation reference.
Method according to embodiment 14 removes the trace impurity in the synthesis gas, and different is, when removing carbonyl metal compound, does not pass into oxygen in the synthesis gas that enters described adsorption tower 2, that is, the concentration of oxygen is 1ppm.Within two weeks of cleaning test, adopting in the synthesis gas after above-mentioned condition purifies, the concentration of sulphur is always≤concentration of 5ppb, ammonia is always≤concentration of 0.05ppm, hydrogen chloride is always≤concentration of 0.01ppm, carbonyl metal compound is always≤and the concentration of 28ppb (in Fe, Ni), oxygen is always≤0.01ppm.
Comparative Examples 5
This embodiment is used for the method that removes the synthesis gas trace impurity of explanation reference.
Method according to embodiment 15 removes the trace impurity in the synthesis gas, different is, when removing carbonyl metal compound, use after 1 year, stop oxygen, the concentration of carbonyl metal compound is very fast in the synthesis gas after then purifying rises to 30ppb (in Fe, Ni) from 5ppb (in Fe, Ni).Recover oxygenation so that after the oxygen that synthesis gas self contains was 150ppm with the oxygen concentration sum that adds, the concentration of carbonyl metal compound was down to below the 5ppb (in Fe, Ni) very soon in the decontaminating syngas.
Comparative Examples 6
This embodiment is used for the method that removes the synthesis gas trace impurity of explanation reference.
Method according to embodiment 15 removes the trace impurity in the synthesis gas, different is when removing carbonyl metal compound, to use after 2 years, stop oxygen, the concentration of carbonyl metal compound progressively rises to 1ppm (in Fe, Ni) in the synthesis gas after then purifying.
Comparative Examples 7
This embodiment is used for the method that removes the synthesis gas trace impurity of explanation reference.
Method according to Comparative Examples 6 removes the trace impurity in the synthesis gas, different is, when removing carbonyl metal compound, use after 2 years, stop oxygen and reaction temperature is brought up to 90 ℃, the concentration of carbonyl metal compound progressively rises to 1.8ppm (in Fe, Ni) in the synthesis gas after then purifying.
Can find out from the result of embodiment 1-17 and Comparative Examples 1-7, adopt method of the present invention impurity in the synthesis gas can be removed effectively.Can find out from the contrast of embodiment 1-3 and Comparative Examples 1-2, when the concentration of oxygen during greater than 50ppm, just carbonyl metal compound can be purified to less than 5.0ppb, and excessive oxygen is helpless to declining to a great extent of carbonyl metal compound content, on the contrary, also can increase the load of follow-up deoxidation tower.Can find out H in the synthesis gas from the contrast of embodiment 1 and embodiment 4
2Purify the afterwards almost not impact of concentration of carbonyl metal compound with the comparing of concentration of CO.Can find out that from the contrast of embodiment 1 and embodiment 11 the active carbon specific area can reduce greatly the content that purifies rear carbonyl metal compound.Can find out to have the different activities charcoal of identical specific area from the contrast of embodiment 1 and embodiment 12, clean-up effect is also different; Cocoanut active charcoal is conducive to reduce the content that purifies rear carbonyl metal compound.
Claims (12)
1. method that removes trace impurity in the synthesis gas, described trace impurity contains carbonyl metal compound, oxygen, cos, hydrogen sulfide and hydrogen chloride, the method comprises carbonyl metal compound, oxygen, cos, hydrogen sulfide and hydrogen chloride is removed from described synthesis gas, it is characterized in that, the method that removes described carbonyl metal compound is included under the existence of oxygen, described synthesis gas is contacted with adsorbent, and the condition of contact and the concentration of oxygen make the carbonyl metal compound that is adsorbed agent absorption be oxidized to metal oxide; Take the concentration of the described oxygen of mol as 50-500ppm, in the concentration of carbonyl metal compound in the described synthesis gas of mol less than 10ppm.
2. method according to claim 1, wherein, take the concentration of the described oxygen of mol as 50-250ppm, the concentration of carbonyl metal compound is as 5ppb-5ppm in the described synthesis gas of mol.
3. method according to claim 1, wherein, the condition that described synthesis gas contacts with adsorbent comprises that the temperature of contact is 50-250 ℃, and the pressure of contact is 0.1-10MPa, and volume space velocity is 500-6000h during the gas of synthesis gas
-1
4. method according to claim 3, wherein, the temperature of described contact is 50-150 ℃, and the pressure of contact is 0.1-5MPa, and volume space velocity is 800-3000h during the gas of synthesis gas
-1
5. method according to claim 1, wherein, described adsorbent is active carbon, and/or described adsorbent comprises carrier and loads on active component on the described carrier; Take the gross mass of described adsorbent as benchmark, the content of described active component is the 10-50 % by weight, and the content of described carrier is the 50-90 % by weight.
6. method according to claim 5, wherein, described active component is the mixture of cupric oxide and zinc oxide, described carrier is active carbon; Take the gross mass of described adsorbent as benchmark, the content of described cupric oxide is the 3-20 % by weight, and the content of described zinc oxide is the 10-30 % by weight, and the content of described active carbon is the 60-85 % by weight.
7. method according to claim 1 wherein, removes oxygen and cos and carries out simultaneously, and the method that removes oxygen and cos comprises and will remove synthesis gas and the PtS of carbonyl metal compound
XThe catalyst contact, the condition of contact is so that oxygen conversion is water, and cos conversion is hydrogen sulfide.
8. method according to claim 7, wherein, described synthesis gas and PtS
XThe condition of catalyst contact comprises that the temperature of contact is 150-200 ℃, and the pressure of contact is 2-5MPa, and volume space velocity is 1000-2000h during the gas of synthesis gas
-1Preferably, the temperature of described contact is 180-190 ℃, and the pressure of contact is 2-2.5MPa, and volume space velocity is 1000-1800h during the gas of synthesis gas
-1
9. according to claim 1 or 7 described methods, wherein, the method that removes described hydrogen sulfide comprises that the synthesis gas that will remove carbonyl metal compound, oxygen and cos contacts with desulfurizing agent.
10. method according to claim 1, wherein, the method that removes hydrogen chloride comprises that the synthesis gas that will remove carbonyl metal compound, oxygen, cos and hydrogen sulfide contacts with antichlor.
11. method according to claim 1, wherein, described trace impurity also contains ammonia, and the method also is included in and removes before the described carbonyl metal compound, and described ammonia is removed.
12. a synthesis gas is characterized in that as the application of producing at least a raw material in hutanal, isobutylaldehyde, n-butanol, isobutanol and the isooctanol described synthesis gas is that the described method of any one is processed the synthesis gas that obtains among the claim 1-11.
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| CN113509815A (en) * | 2021-04-19 | 2021-10-19 | 中冶长天国际工程有限责任公司 | Method for regulating and controlling circulation quantity of activated carbon in sintering flue gas multi-pollutant treatment |
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