CN103432896B - A kind of cleanser and Synthesis and applications thereof removing impurity oxygen in the reducibility gas such as synthesis gas - Google Patents
A kind of cleanser and Synthesis and applications thereof removing impurity oxygen in the reducibility gas such as synthesis gas Download PDFInfo
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- CN103432896B CN103432896B CN201310371387.7A CN201310371387A CN103432896B CN 103432896 B CN103432896 B CN 103432896B CN 201310371387 A CN201310371387 A CN 201310371387A CN 103432896 B CN103432896 B CN 103432896B
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Abstract
The invention discloses a kind of cleanser and the Synthesis and applications thereof that remove impurity oxygen in the reducibility gas such as synthesis gas, cleanser is made up of active component and carrier, the general formula of described cleanser is CuZnCa (O)-carrier, wherein in CuZnCa (O), mol ratio is Cu/Zn/Ca=1/ (0.05 ~ 0.4)/(0.2 ~ 0.7), carrier/CuO=(1.8 ~ 2.3)/1 in mass ratio.Preparation method is coprecipitation.The application of cleanser: reaction temperature is 110 DEG C ~ 320 DEG C, and reaction pressure is 0Mpa ~ 6.0Mpa, and reaction velocity is 100h
-1~ 10000h
-1.The present invention is under the prerequisite that production cost is lower, and guarantee that the smart deoxidier produced has higher pressure measurement intensity, after purification, gas remaining oxygen is lower simultaneously, adapts to the requirement of the reducibility gas imurity-removal oxygen such as current synthesis gas with this.
Description
Technical field
The invention belongs to gas purifying agent and Synthesis and applications field thereof, more specifically to a kind of cleanser and the Synthesis and applications thereof that remove impurity oxygen in the reducibility gas such as synthesis gas.
Background technology
Synthesis gas be a kind of with carbon monoxide, hydrogen for key component, purposes is material gas very widely.The source wide range of synthesis gas, can be vaporized by the solid fuel such as coal or coke and produce, also can produce through the light hydrocarbons such as natural gas, naphtha, can also be produced by heavy oil through partial oxidation process.
During production synthesis gas, not only generate the useful component such as carbon monoxide, hydrogen, also create some poisonous and harmful substance, such as: impurity oxygen.In synthesis gas, impurities oxygen can react with carbonyl compounds the acid generating and suppress carbongl group synthesis reaction, and oxidation promoters, makes it generate complex compound without catalytic action, high-boiling components is accumulated, reduces reaction effect.In addition production High Purity Hydrogen, high-purity CO, wherein oxygen content is also an important performance assessment criteria.
Remove in the report of the cleanser of impurity oxygen in the reducibility gas such as synthesis gas existing, CN 1220302A discloses a kind of with active carbon or γ-Al
2o
3for carrier, using the oxide of copper, manganese, cobalt as active component, adopt cleanser prepared by infusion process.This cleanser reaction temperature 110 DEG C ~ 150 DEG C, reaction velocity 1000 ~ 2000h
-1, deoxidation can be carried out to the high-concentration carbon monoxide gas of < 1% oxygen content, purified gas remaining oxygen < 1*10
-6.
It is carrier with activated alumina that CN 1332753C discloses a kind of, using the oxide of noble metal platinum, molybdenum as active component, adopts cleanser prepared by infusion process.This cleanser needs prereduction before using, reaction temperature 190 DEG C after reduction, and reaction velocity 8000h
-1, can be 2000*10 to oxygen content
-6synthesis gas carry out deoxidation, purified gas remaining oxygen is 0.04*10
-6.
The problem that gas remaining oxygen is higher after cleaning is all deposited in the base metal deoxidier of existing report, and the noble metal deoxidier of existing report, although gas remaining oxygen can reach 0.04*10 after purification
-6, but there is the too high problem of production cost.
Summary of the invention
The object of the invention is to: provide a kind of and there is the higher cleanser removing precision, to adapt to the requirement of the reducibility gas imurity-removal oxygen such as current synthesis gas.Another object of the present invention is to provide preparation method and the application thereof of this cleanser.
The object of the invention is realized by following technical proposals:
A kind of cleanser removing impurity oxygen in the reducibility gas such as synthesis gas, be made up of active component and carrier, the general formula of described cleanser is CuZnCa (O)-carrier, wherein in CuZnCa (O), mol ratio is Cu/Zn/Ca=1/ (0.05 ~ 0.4)/(0.2 ~ 0.7), carrier/CuO=(1.8 ~ 2.3)/1 in mass ratio.
As selection, in described CuZnCa (O), mol ratio is Cu/Zn/Ca=1/ (0.07 ~ 0.35)/(0.25 ~ 0.65), carrier/CuO=(1.4 ~ 2.1)/1 in mass ratio.
As further selection, in described CuZnCa (O), mol ratio is Cu/Zn/Ca=1/ (0.1 ~ 0.19)/(0.27 ~ 0.63), carrier/CuO=(1.5 ~ 2)/1 in mass ratio.
The aforementioned preparation method removing the cleanser of impurity oxygen in the reducibility gas such as synthesis gas, comprises the following steps successively:
A the mixed aqueous solution A of Ni metal, Zn, Ca soluble salt mixes with the aqueous solution B of precipitating reagent and makes it that precipitation reaction occur to generate slurry C by ();
(b) aging slurry C;
C carrier that () adds aequum in slurry C is purified agent precursor D;
D () filtration, purification agent precursor D is purified agent presoma E;
E () is dry under 50 DEG C ~ 110 DEG C conditions by cleanser presoma E, roasting under 300 DEG C ~ 450 DEG C conditions, shapingly namely obtains required cleanser.
As selection, the soluble salt of Ni metal described in step (a), Zn, Ca is nitrate, and precipitating reagent described in step (a) is sodium carbonate.
As selection, described carrier is active carbon, and this carrier can assist other components of cleanser to remove micro amount of oxygen at reaction conditions better.
The aforesaid application removing the cleanser of impurity oxygen in the reducibility gas such as synthesis gas, operating condition is: reaction temperature is 170 DEG C ~ 300 DEG C, and reaction pressure is 0 Mpa ~ 2.0Mpa, and reaction velocity is 500 h
-1~ 8000h
-1.
As selection, operating condition is: reaction temperature is 160 DEG C ~ 310 DEG C, and reaction pressure is 0Mpa ~ 5.5Mpa, and reaction velocity is 200h
-1~ 9000h
-1.
As further selection, reaction temperature is 170 DEG C ~ 300 DEG C, and reaction pressure is 0Mpa ~ 5.0Mpa, and reaction velocity is 500h
-1~ 8000h
-1.
Beneficial effect of the present invention: two difficult problems that the invention solves prior art, ensure that the pressure measurement intensity of cleanser is higher simultaneously, namely under the prerequisite that production cost is lower, guarantee that the smart deoxidier produced has higher pressure measurement intensity, after purification, gas remaining oxygen is lower simultaneously, adapts to the requirement of the reducibility gas imurity-removal oxygen such as current synthesis gas with this.Cleanser of the present invention is compared with other similar cleansers, because the present invention adopts precipitation of joint sedimentation to prepare cleanser, so cleanser has higher active component content and higher pressure measurement intensity, secondly, the present invention adopts Cu, Zn, Ca as the active component of cleanser, the chemisorbed that can improve copper is active, can suppress again the migration of copper, and therefore cleanser of the present invention has higher oxygen removal precision pressure measurement simultaneously intensity > 90 N/cm.When in the reducibility gas such as synthesis gas, oxygen content is≤1%, after cleanser of the present invention removes, in synthesis gas, residual oxygen is lower than 0.01*10
-6.
Detailed description of the invention
Following non-limiting examples is for illustration of the present invention.
In each embodiment, cleanser activity rating method is: before reaction, cleanser is through H
2-N
2gaseous mixture reduces, air speed 800h
-1, reduction temperature 240 DEG C, terminates used time 24h from room temperature to final reduction.Switch to (H subsequently
2the volume ratio of/CO is 1.5 ~ 2.5, oxygen content≤1%) synthesis gas or hydrogen (oxygen content≤1%) or high-concentration carbon monoxide gas (oxygen content≤1%), be 0 Mpa ~ 2.0Mpa in reaction pressure, reaction temperature is 170 DEG C ~ 300 DEG C, and reaction velocity is 500 h
-1~ 8000h
-1condition under remove impurity oxygen in the reducibility gas such as synthesis gas, the residual oxygen in the reducibility gas such as the synthesis gas after purification adopts trace oxygen analyzer to detect.
embodiment 1:
By 149.83g Cu (NO
3)
23H
2o, 18.45gZn (NO
3)
26H
2o and 39.54gCa (NO
3)
24H
2o is made into 1500ml mixing salt solution, with 0.4mol/L ~ 1.0mol/L sodium carbonate liquor co-precipitation under 65 DEG C ~ 70 DEG C conditions, pH value is 7.0 ~ 7.5, active carbon is added after aging 1h ~ 2h, added active carbon and CuO mass ratio are 1.5/1, after filtration, deionized water washs to obtain solid, dry 16h, 350 DEG C of calcining 4h at 50 DEG C, compressing tablet, obtained cleanser DI-a.Remove the impurity oxygen in synthesis gas with this cleanser, wherein oxygen content≤1%, reaction temperature is 170 DEG C, and reaction pressure is normal pressure, and reaction velocity is 500h
-1.Through cleanser imurity-removal oxygen, oxygen content < 0.01*10 in synthesis gas
-6.Remove the impurity oxygen in hydrogen with this cleanser, wherein oxygen content≤1%, reaction temperature is 170 DEG C, and reaction pressure is normal pressure, and reaction velocity is 500h
-1.Through cleanser imurity-removal oxygen, oxygen content < 0.01*10 in hydrogen
-6.Remove the impurity oxygen in high-concentration carbon monoxide gas with this cleanser, wherein oxygen content≤1%, reaction temperature is 170 DEG C, and reaction pressure is normal pressure, and reaction velocity is 500h
-1.Through cleanser imurity-removal oxygen, oxygen content < 0.01*10 in high-concentration carbon monoxide gas
-6.
embodiment 2:
By 149.83g Cu (NO
3)
23H
2o, 43.35gZn (NO
3)
26H
2o and 65.9gCa (NO
3)
24H
2o is made into 1500ml mixing salt solution, with 0.4mol/L ~ 1.0mol/L sodium carbonate liquor co-precipitation under 65 DEG C ~ 70 DEG C conditions, pH value is 7.0 ~ 7.5, active carbon is added after aging 1h ~ 2h, added active carbon and CuO mass ratio are 1.75/1, after filtration, deionized water washs to obtain solid, dry 16h, 375 DEG C of calcining 4h at 75 DEG C, compressing tablet, obtained cleanser DI-b.Remove the impurity oxygen in synthesis gas with this cleanser, wherein oxygen content≤1%, reaction temperature is 235 DEG C, and reaction pressure is 1.0Mpa, and reaction velocity is 4250h
-1.Through cleanser imurity-removal oxygen, oxygen content < 0.01*10 in synthesis gas
-6.Remove the impurity oxygen in hydrogen with this cleanser, wherein oxygen content≤1%, reaction temperature is 235 DEG C, and reaction pressure is 2.5Mpa, and reaction velocity is 4250h
-1.Through cleanser imurity-removal oxygen, oxygen content < 0.01*10 in hydrogen
-6.Remove the impurity oxygen in high-concentration carbon monoxide gas with this cleanser, wherein oxygen content≤1%, reaction temperature is 235 DEG C, and reaction pressure is 1.0Mpa, and reaction velocity is 4250h
-1.Through cleanser imurity-removal oxygen, oxygen content < 0.01*10 in high-concentration carbon monoxide gas
-6.
embodiment 3:
By 149.83g Cu (NO
3)
23H
2o, 68.25gZn (NO
3)
26H
2o and 92.26gCa (NO
3)
24H
2o is made into 1500ml mixing salt solution, with 0.4mol/L ~ 1.0mol/L sodium carbonate liquor co-precipitation under 65 DEG C ~ 70 DEG C conditions, pH value is 7.0 ~ 7.5, active carbon is added after aging 1h ~ 2h, added active carbon and CuO mass ratio are 2/1, after filtration, deionized water washs to obtain solid, dry 8h, 450 DEG C of calcining 4h at 110 DEG C, compressing tablet, obtained cleanser DI-c.Remove the impurity oxygen in synthesis gas with this cleanser, wherein oxygen content≤1%, reaction temperature is 300 DEG C, and reaction pressure is 2.0Mpa, and reaction velocity is 8000h
-1.Through cleanser imurity-removal oxygen, oxygen content < 0.01*10 in synthesis gas
-6.Remove the impurity oxygen in hydrogen with this cleanser, wherein oxygen content≤1%, reaction temperature is 300 DEG C, and reaction pressure is 5.0Mpa, and reaction velocity is 8000h
-1.Through cleanser imurity-removal oxygen, oxygen content < 0.01*10 in hydrogen
-6.Remove the impurity oxygen in high-concentration carbon monoxide gas with this cleanser, wherein oxygen content≤1%, reaction temperature is 300 DEG C, and reaction pressure is 2.0Mpa, and reaction velocity is 8000h
-1.Through cleanser imurity-removal oxygen, oxygen content < 0.01*10 in high-concentration carbon monoxide gas
-6.
embodiment 4:
By 149.83g Cu (NO
3)
23H
2o, 26.75gZn (NO
3)
26H
2o and 65.9gCa (NO
3)
24H
2o is made into 1500ml mixing salt solution, with 0.4mol/L ~ 1.0mol/L sodium carbonate liquor co-precipitation under 65 DEG C ~ 70 DEG C conditions, pH value is 7.0 ~ 7.5, active carbon is added after aging 1h ~ 2h, added active carbon and CuO mass ratio are 1.75/1, after filtration, deionized water washs to obtain solid, dry 16h, 375 DEG C of calcining 4h at 75 DEG C, compressing tablet, obtained cleanser DI-b.Remove the impurity oxygen in synthesis gas with this cleanser, wherein oxygen content≤1%, reaction temperature is 235 DEG C, and reaction pressure is 1.0Mpa, and reaction velocity is 4250h
-1.Through cleanser imurity-removal oxygen, oxygen content < 0.01*10 in synthesis gas
-6.Remove the impurity oxygen in hydrogen with this cleanser, wherein oxygen content≤1%, reaction temperature is 235 DEG C, and reaction pressure is 2.5Mpa, and reaction velocity is 4250h
-1.Through cleanser imurity-removal oxygen, oxygen content < 0.01*10 in hydrogen
-6.Remove the impurity oxygen in high-concentration carbon monoxide gas with this cleanser, wherein oxygen content≤1%, reaction temperature is 235 DEG C, and reaction pressure is 1.0Mpa, and reaction velocity is 4250h
-1.Through cleanser imurity-removal oxygen, oxygen content < 0.01*10 in high-concentration carbon monoxide gas
-6.
embodiment 5:
By 149.83g Cu (NO
3)
23H
2o, 35.05gZn (NO
3)
26H
2o and 92.26gCa (NO
3)
24H
2o is made into 1500ml mixing salt solution, with 0.4mol/L ~ 1.0mol/L sodium carbonate liquor co-precipitation under 65 DEG C ~ 70 DEG C conditions, pH value is 7.0 ~ 7.5, active carbon is added after aging 1h ~ 2h, added active carbon and CuO mass ratio are 2/1, after filtration, deionized water washs to obtain solid, dry 8h, 450 DEG C of calcining 4h at 110 DEG C, compressing tablet, obtained cleanser DI-c.Remove the impurity oxygen in synthesis gas with this cleanser, wherein oxygen content≤1%, reaction temperature is 300 DEG C, and reaction pressure is 2.0Mpa, and reaction velocity is 8000h
-1.Through cleanser imurity-removal oxygen, oxygen content < 0.01*10 in synthesis gas
-6.Remove the impurity oxygen in hydrogen with this cleanser, wherein oxygen content≤1%, reaction temperature is 300 DEG C, and reaction pressure is 5.0Mpa, and reaction velocity is 8000h
-1.Through cleanser imurity-removal oxygen, oxygen content < 0.01*10 in hydrogen
-6.Remove the impurity oxygen in high-concentration carbon monoxide gas with this cleanser, wherein oxygen content≤1%, reaction temperature is 300 DEG C, and reaction pressure is 2.0Mpa, and reaction velocity is 8000h
-1.Through cleanser imurity-removal oxygen, oxygen content < 0.01*10 in high-concentration carbon monoxide gas
-6.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (5)
1. one kind removes the application of the cleanser of impurity oxygen in synthesis gas, cleanser is made up of active component and carrier, the general formula of described cleanser is CuZnCa (O)-carrier, wherein in CuZnCa (O), mol ratio is Cu/Zn/Ca=1/ (0.05 ~ 0.4)/(0.2 ~ 0.7), carrier/CuO=(1.8 ~ 2.3)/1 in mass ratio, it is characterized in that: operating condition is: reaction temperature is 110 DEG C ~ 320 DEG C, reaction pressure is 0 Mpa ~ 6.0Mpa, and reaction velocity is 100 h
-1~ 10000h
-1.
2. remove the application of the cleanser of impurity oxygen in synthesis gas as claimed in claim 1, it is characterized in that: operating condition is: reaction temperature is 160 DEG C ~ 310 DEG C, and reaction pressure is 0Mpa ~ 5.5Mpa, and reaction velocity is 200h
-1~ 9000h
-1.
3. the application removing the cleanser of impurity oxygen in synthesis gas according to claim 2, is characterized in that: operating condition is: reaction temperature is 170 DEG C ~ 300 DEG C, and reaction pressure is 0Mpa ~ 5.0Mpa, and reaction velocity is 500h
-1~ 8000h
-1.
4. remove the application of the cleanser of impurity oxygen in synthesis gas as claimed in claim 1, it is characterized in that: in described CuZnCa (O), mol ratio is Cu/Zn/Ca=1/ (0.07 ~ 0.35)/(0.25 ~ 0.65), carrier/CuO=(1.4 ~ 2.1)/1 in mass ratio.
5. remove the application of the cleanser of impurity oxygen in synthesis gas as claimed in claim 4, it is characterized in that: in described CuZnCa (O), mol ratio is Cu/Zn/Ca=1/ (0.1 ~ 0.19)/(0.27 ~ 0.63), carrier/CuO=(1.5 ~ 2)/1 in mass ratio.
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CN102390807A (en) * | 2011-08-10 | 2012-03-28 | 西南化工研究设计院 | Copper series purifying agent and preparation method thereof |
CN102814160A (en) * | 2012-08-20 | 2012-12-12 | 西南化工研究设计院有限公司 | Cleaning agent for removing iron carbonyl and nickel carbonyl in synthesis gas and preparation method and application of cleaning agent |
CN102872883A (en) * | 2012-09-26 | 2013-01-16 | 中国科学院山西煤炭化学研究所 | Supported non-noble metal oxygen-containing coalbed methane deoxidation catalyst and preparation method and application thereof |
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2013
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CN101224871A (en) * | 2008-02-03 | 2008-07-23 | 湖北省化学研究院 | Deeply purifying method for synthetic gas |
CN101322942A (en) * | 2008-07-29 | 2008-12-17 | 西南化工研究设计院 | Oxygen-containing coal bed gas deoxidation catalyst and preparation thereof as well as applications |
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