CN102872881A - Copper-based catalyst used in process of synthesizing low carbon mixed alcohol and preparation method and application of catalyst - Google Patents
Copper-based catalyst used in process of synthesizing low carbon mixed alcohol and preparation method and application of catalyst Download PDFInfo
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Abstract
The invention relates to a copper-based catalyst used in the process of synthesizing low carbon mixed alcohol. The catalyst consists of 25 to 40 molar percent of Cu, 25 to 40 molar percent of Mn, 1 to 10 molar percent of Fe, 5 to 20 molar percent of Zn, 0.5 to 5 molar percent of Cr, 10 to 30 molar percent of Zr and 0.05 to 2 molar percent of K. The catalyst has the advantages of high selectivity and activity and long service life.
Description
Technical field
The invention belongs to a kind of preparation method and application of catalyst, relate in particular to a kind of catalyst and preparation method and application of preparing low-carbon mixed alcohol by synthetic gas.
Background technology
The energy is the lifeblood of the national economic development, since the continuous consumption of natural resources especially oil crisis, has actively sought and develops new energy system and chemical products have been put very urgent position.The national statistics data show that since 1993, China became net importer by oil net exporter, and China's Imported oil was broken through 200,000,000 tons of high pointes first in 2007, reached 20544.2 ten thousand tons.According to International Energy Agency's prediction, will be above 76.9% to the Overseas Oil interdependency to the year two thousand twenty China.National energy develops 12 planning and has clearly proposed the new approaches that promote production of energy and utilize mode to change: " adhere to economization at first, base on our country, diverse development, protection of the environment; strengthen international mutual beneficial co-operation; adjust Optimization of Energy Structure, make up safety, stable, economic, the modern energy industry system that cleans.”
Research is with coal and natural gas base synthesis gas (CO+H
2) fuels and chemicals processed is the C-1 chemistry on basis, the industrial applications of implementation procedure reduces the dependence to limited petroleum resources, for the guarantee of economic development, environmental protection especially national energy security all tool be of great significance.C-1 chemistry has formed the process system than horn of plenty at present, is its main research by synthesis gas synthesis of chemicals and fuel.Meanwhile, coal gasification preparing synthetic gas technology is being moved towards to maximize and is practical, for the comprehensive utilization of synthesis gas provides cheap, formed suitable unstripped gas, for the commercial Application of promotion synthesis gas has been created ripe condition.Producing MAS (the alcohols mixture of C1-C6) as the basis by synthesis gas take coal and natural gas is one of important content of C-1 chemistry, and its technological process is substantially similar with the high pressure synthesizing methanol.The MAS main application is as the additive of clean gasoline or directly acts as a fuel that to replace leaded additive, its effect mainly is to increase oxygen content, promotes the clean burning of fuel, improves the octane number of fuel.In addition, after the MAS separation, can obtain first, second, third, fourth, amylalcohol, except as solvent and the esterifying reagent, also can be used as the raw material of chemical products.Moreover MAS itself is a kind of good clean fuel, has abroad developed take methyl alcohol as main " methyl fuel " and take ethanol as main " ethylized fuel ".Therefore, will have wide market prospects by the synthetic developmental research that mixes low-carbon alcohols of CO hydrogenation.
The related catalyst of this process mainly contains four large classes at present: the catalst for synthesis of methanol of (1) modification: this type of catalyst series catalyst for synthesizing methanol is (such as low temperature Cu/ZnO/Al
2O
3, high temperature Zn/Cr
2O
3Deng) add an amount of alkali metal or Modified With Alkali-earth Compounds and get, more typical patent has the people such as EP-0034338-A2(C.E. Hofstadt) and United States Patent (USP) 4513100(Snam company subsidize, inventing the people is the people such as Fattore).Although this type of catalyst activity is higher, and isobutanol content is higher in the product, but shortcoming is severe reaction conditions (pressure is 14-20MPa, and temperature is 350-450 ℃), higher alcohol is low (being generally less than 35%) selectively, water content high (being generally 30-50%) in the product; (2) copper-cobalt catalyst agent: France Petroleum Institute (IFP) has at first developed Cu-Co co-precipitation low carbon mixed alcohol catalyst, (US 4122110 only just to obtain four catalyst patents in 1985,4291126 and GB 2118061,2158730), the synthetic product of this type of catalyst is mainly C
1-C
6The straight chain n-alkanol, accessory substance is mainly C
1-C
6Aliphatic hydrocarbon, reaction condition is similar to low pressure methanol synthesis catalyst.The shortcoming of this catalyst is less stable.(3) Rh catalyst based (such as US 4014913 and 4096164): after adding one to two kind of transition metal or metal oxide auxiliary agent in the support type Rh catalyst, to low-carbon alcohols is synthetic higher activity and selectivity, particularly C arranged
2 +The selective height of alcohol, product is take ethanol as main.But the Rh compound is expensive, and catalyst is easily by CO
2Poison, its activity and selectivity does not generally reach industrial requirement.(4) MoS
2Catalyst: this type of catalyst is that the molybdenum of U.S. DOW company exploitation is sulfide (main patent is seen the people's such as Stevens US 4882360), this catalyst system not only has anti-sulphur, and the product water content is few, and higher alcohol content is higher, reaching 30-70%, wherein mainly is ethanol and normal propyl alcohol.This catalyst Main Problems be wherein auxiliary element very easily and form carbonyls between the CO, cause the loss of auxiliary element, affect the activity and selectivity of catalyst, cause catalyst stability and life-span to be restricted.
Chinese invention patent CN101185899A discloses a kind of novel copper base synthesizing low carbon mixed alcohol catalyst, generally speaking, still has total alcohol shortcomings such as selectively distribution on the low side, the higher alcohol product is relatively poor, still has a certain distance from industrial applications.
Summary of the invention
The present invention provides a kind of selectively good mainly for the shortcoming of above-mentioned catalyst, and the life-span is long, active high copper-based catalysts and preparation method and application.
Catalyst molar percentage of the present invention consists of:
Cu：25-40%，Mn：25-40%，Fe：1-10%，?Zn：5-20%，
Cr：0.5-5%，Zr：10-30%，K：0.05-2%。
Method for preparing catalyst provided by the invention may further comprise the steps:
(1) with the in mass ratio ratio mixing of 2～4:1:1～0.5 of surfactant, cosurfactant and oil phase, the formation oil-phase solution stirs;
(2) nitrate of getting in addition Cu, Mn, Fe, Zn, Cr, Zr is dissolved in the isopyknic distilled water of mentioned solution to form mixed solution, the speed of this solution by 2～20mL/min is dropped in step (1) oil-phase solution, stir while dripping, be made into microemulsion system;
(3) then the alkaline solution of preparation 0.1-1.0mol/L drops to above-mentioned microemulsion system to pH value and is till 7～10;
(4) step (3) gains are lower aging 1-24 hour at 25-80 ℃, after the 1000-5000r/min centrifuge separates 5-30min, to the obvious oil phase of sediment surface nothing and surfactant, be washed with distilled water to again till the neutrality with absolute ethanol washing;
(5) potash is dissolved in the isopyknic distilled water of step (4) sediment after, add the sediment of step (4) gained, and stir into pastel, after 40-150 ℃ of drying 300-550 ℃ roasting 1-6 hour, obtain catalyst after compressing tablet sieves.
Aforesaid surfactant is softex kw (CTAB), dioctadecyl dimethyl ammonium chloride (DODMAC), Triton X-100 (Triton X-100), dioctyl sodium sulfosuccinate (AOT), dodecyl sodium sulfate (SDS), neopelex (DBS), a kind of in the lauryl alcohol polyoxyethylene sodium sulphate (AES).
Aforesaid cosurfactant is a kind of in n-butanol, n-amyl alcohol, n-hexyl alcohol, n-heptanol, n-octyl alcohol, Decanol, the n-dodecanol.
Aforesaid oil phase is a kind of in hexane, heptane, octane, cyclohexane, cycloheptane or the cyclooctane.
Aforesaid alkaline solution is a kind of in sodium carbonate, potash or the ammoniacal liquor.
The application conditions of catalyst of the present invention is: reaction temperature T=200-300 ℃, and pressure p=2.0-8.0MPa, gas space velocity GHSV=500-10000h
-1, H
2/ CO(mol ratio)=0.5-3.0.
The present invention compared with prior art has following features:
(1) the copper-based catalysts narrow diameter distribution that adopts microemulsion method to prepare obtains the uniform nanoparticle of particle diameter easily, and each component interphase interaction is strong, good stability, and especially strong synergy is very beneficial for the synthetic of low-carbon alcohols between active component.
(2) catalyst dry powder is easy to moulding, and mechanical strength is good, is suitable for industry and amplifies.
(3) reaction condition is gentle, and strong adaptability can use under the working condition comparatively widely.
(4) adopt the prepared copper-based catalysts of the present invention for the synthesis of gas synthesizing low-carbon mixed alcohol, C
2 +Alcohol selectively can reach more than 60%, and the space-time yield of alcohol can be greater than 0.3g/mL.h.
The specific embodiment
Embodiment 1
Take by weighing respectively cyclohexane 100g, softex kw 50g, n-butanol 25g stirs the formation oil-phase solution; Other takes off the row metal nitrate by mole% Cu 40%, Mn 40%, Fe 1%, Zn 5%, Cr 0.5%, and Zr 13.45% is dissolved in that to form concentration with the isopyknic distilled water of mentioned solution be the mixed solution of 0.1mol/L, and this solution is dropped to above-mentioned oil-phase solution by the speed of 2mL/min, stir while dripping, be made into microemulsion system.Other gets sodium carbonate and is mixed with 30% solution, drop to above-mentioned microemulsion system to pH value and be till 7.0, react this mixed solution is aging 24 hours at 25 ℃ after complete, behind the 5000r/min centrifugation 10min, remove the upper strata stillness of night,, to the obvious oil phase of sediment surface nothing and surfactant, be washed with distilled water to till the neutrality again with absolute ethanol washing.With the 0.05%(molar percentage) potassium (with the form of potash) is dissolved in distilled water (with the sediment equal-volume), adds the sediment of above-mentioned gained and stir to form pastel, and 400 ℃ of roasting 2h estimate after compressing tablet sieves after 40 ℃ of dryings.Each weight metal percentage composition is Cu:39.86%, Mn:34.46%, Fe:0.88%, Zn:5.13%, Cr:0.41%, Zr:19.23%, K:0.03%.The CO hydrogenation reaction is carried out at continuous fixed bed reactor, loaded catalyst 2mL, before reaction first with synthesis gas the lower reduction of normal pressure, 300 ℃ 12 hours, be down to and transfer to appropraite condition after the room temperature and react.Service condition is: T=240 ℃, and p=4.0MPa, GHSV=6000h
-1, H
2/ CO(mol ratio)=2.0.The product chromatography of after refrigerated separation, taking a sample, the result is as follows:
Embodiment 2
Take by weighing respectively hexane 100g, Triton X-100 (Triton X-100) 25g, n-amyl alcohol 25g stirs the formation oil-phase solution; Other takes off the row metal nitrate by mole% Cu 40%, Mn 30%, Fe 1%, Zn 10%, Cr 2%, and Zr 16.5% is dissolved in that to form concentration with the isopyknic distilled water of mentioned solution be the mixed solution of 0.2mol/L, and this solution is dropped to above-mentioned oil-phase solution by the speed of 5mL/min, stir while dripping, be made into microemulsion system.Other gets sodium carbonate and is mixed with 30% solution, drop to above-mentioned microemulsion system to pH value and be till 8.0, react complete after with this mixed solution at 50 ℃ of aging 3h, behind the 1000r/min centrifugation 30min, remove the upper strata stillness of night,, to the obvious oil phase of sediment surface nothing and surfactant, be washed with distilled water to till the neutrality again with absolute ethanol washing.With the 0.5%(molar percentage) potassium (with the form of potash) is dissolved in distilled water (with the sediment equal-volume), adds the sediment of above-mentioned gained and stir to form pastel, and 300 ℃ of roasting 6h estimate after compressing tablet sieves after 80 ℃ of dryings.Each weight metal percentage composition is Cu:38.94%, Mn:25.25%, Fe:0.86%, Zn:10.01%, Cr:1.59%, Zr:23.05%, K:0.30%.The CO hydrogenation reaction is carried out at continuous fixed bed reactor, loaded catalyst 2mL, before reaction first with synthesis gas the lower reduction of normal pressure, 300 ℃ 12 hours, be down to and transfer to appropraite condition after the room temperature and react.Service condition is: T=260 ℃, and p=6.0MPa, GHSV=4000h
-1, H
2/ CO(mol ratio)=3.0.The product chromatography of after refrigerated separation, taking a sample, the result is as follows:
Embodiment 3
Take by weighing respectively heptane 100g, dioctadecyl dimethyl ammonium chloride (DODMAC) 33.3g, n-hexyl alcohol 33.3g stirs the formation oil-phase solution; Other takes off the row metal nitrate by mole% Cu 40%, Mn 25%, Fe 5%, Zn 20%, Cr 5%, and Zr 4% is dissolved in that to form concentration with the isopyknic distilled water of mentioned solution be the mixed solution of 0.5mol/L, and this solution is dropped to above-mentioned oil-phase solution by the speed of 10mL/min, stir while dripping, be made into microemulsion system.Other gets potash and is mixed with 30% solution, drop to above-mentioned microemulsion system to pH value and be till 8.5, react complete after with this mixed solution at 80 ℃ of aging 1h, behind the 3000r/min centrifugation 10min, remove the upper strata stillness of night,, to the obvious oil phase of sediment surface nothing and surfactant, be washed with distilled water to till the neutrality again with absolute ethanol washing.With the 1%(molar percentage) potassium (with the form of potash) is dissolved in distilled water (with the sediment equal-volume), adds the sediment of above-mentioned gained and stir to form pastel, and 450 ℃ of roasting 2h estimate after compressing tablet sieves after 120 ℃ of dryings.Each weight metal percentage composition is Cu:41.22%, Mn:22.27%, Fe:4.53%, Zn:21.21%, Cr:4.22%, Zr:5.92%, K:0.63%.The CO hydrogenation reaction is carried out at continuous fixed bed reactor, loaded catalyst 2mL, before reaction first with synthesis gas the lower reduction of normal pressure, 300 ℃ 12 hours, be down to and transfer to appropraite condition after the room temperature and react.Service condition is: T=300 ℃, and p=2.0MPa, GHSV=10000h
-1, H
2/ CO(mol ratio)=2.0.The product chromatography of after refrigerated separation, taking a sample, the result is as follows:
Embodiment 4
Take by weighing respectively octane 100g, dioctyl sodium sulfosuccinate (AOT) 50g, n-heptanol 50g stirs the formation oil-phase solution; Other takes off the row metal nitrate by mole% Cu 30%, Mn 25%, Fe 10%, Zn 20%, Cr 4%, and Zr 10% is dissolved in that to form concentration with the isopyknic distilled water of mentioned solution be the mixed solution of 0.6mol/L, and this solution is dropped to above-mentioned oil-phase solution by the speed of 15mL/min, stir while dripping, be made into microemulsion system.Other gets 25% ammoniacal liquor and is mixed with 10% solution, drop to above-mentioned microemulsion system to pH value and be till 9.0, react complete after with this mixed solution at 25 ℃ of aging 6h, behind the 5000r/min centrifugation 5min, remove the upper strata stillness of night,, to the obvious oil phase of sediment surface nothing and surfactant, be washed with distilled water to till the neutrality again with absolute ethanol washing.With the 1%(molar percentage) potassium (with the form of potash) is dissolved in distilled water (with the sediment equal-volume), and 550 ℃ of roasting 1h estimate after compressing tablet sieves after 150 ℃ of dryings.Each weight metal percentage composition is Cu:30.23%, Mn:21.78%, Fe:8.86%, Zn:20.74%, Cr:3.30%, Zr:14.47%, K:0.62%.The CO hydrogenation reaction is carried out at continuous fixed bed reactor, loaded catalyst 2mL, before reaction first with synthesis gas the lower reduction of normal pressure, 300 ℃ 12 hours, be down to and transfer to appropraite condition after the room temperature and react.Service condition is: T=240 ℃, and p=6.0MPa, GHSV=1000h
-1, H
2/ CO(mol ratio)=0.5.The product chromatography of after refrigerated separation, taking a sample, the result is as follows:
Embodiment 5
Take by weighing respectively cycloheptane 150g, dodecyl sodium sulfate (SDS) 50g, n-octyl alcohol 50g stirs the formation oil-phase solution; Other takes off the row metal nitrate by mole% Cu 25%, Mn 30%, Fe 10%, Zn 10%, Cr 3%, and Zr 20% is dissolved in that to form concentration with the isopyknic distilled water of mentioned solution be the mixed solution of 0.2mol/L, and this solution is dropped to above-mentioned oil-phase solution by the speed of 20mL/min, stir while dripping, be made into microemulsion system.Other gets 25% ammoniacal liquor and is mixed with 10% solution, drop to above-mentioned microemulsion system to pH value and be till 9.5, react complete after with this mixed solution at 70 ℃ of aging 4h, behind the 4000r/min centrifugation 10min, remove the upper strata stillness of night,, to the obvious oil phase of sediment surface nothing and surfactant, be washed with distilled water to till the neutrality again with absolute ethanol washing.With the 2%(molar percentage) potassium (with the form of potash) is dissolved in distilled water (with the sediment equal-volume), adds the sediment of above-mentioned gained and stir to form pastel, and 400 ℃ of roasting 2h estimate after compressing tablet sieves after 120 ℃ of dryings.Each weight metal percentage composition is Cu:24.41%, Mn:25.33%, Fe:8.58%, Zn:10.05%, Cr:2.40%, Zr:28.03%, K:1.20%.The CO hydrogenation reaction is carried out at continuous fixed bed reactor, loaded catalyst 2mL, before reaction first with synthesis gas the lower reduction of normal pressure, 300 ℃ 12 hours, be down to and transfer to appropraite condition after the room temperature and react.Service condition is: T=200 ℃, and p=8.0MPa, GHSV=500h
-1, H
2/ CO(mol ratio)=1.The product chromatography of after refrigerated separation, taking a sample, the result is as follows:
Embodiment 6
Take by weighing respectively cyclooctane 150g, lauryl alcohol polyoxyethylene sodium sulphate (AES) 50g, n-dodecanol 25g stirs the formation oil-phase solution; Other takes off the row metal nitrate by mole% Cu 25%, Mn 25%, Fe 5%, Zn 13%, Cr 1%, and Zr 30% is dissolved in that to form concentration with the isopyknic distilled water of mentioned solution be the mixed solution of 0.1mol/L, and this solution is dropped to above-mentioned oil-phase solution by the speed of 5mL/min, stir while dripping, be made into microemulsion system.Other gets potash and is mixed with 30% solution, drop to above-mentioned microemulsion system to pH value and be till 10.0, react complete after with this mixed solution at 50 ℃ of aging 10h, behind the 5000r/min centrifugation 10min, remove the upper strata stillness of night,, to the obvious oil phase of sediment surface nothing and surfactant, be washed with distilled water to till the neutrality again with absolute ethanol washing.With the 1%(molar percentage) potassium (with the form of potash) is dissolved in distilled water (with the sediment equal-volume), adds the sediment of above-mentioned gained and stir to form pastel, and 350 ℃ of roasting 4h estimate after compressing tablet sieves after 80 ℃ of dryings.Each weight metal percentage composition is Cu:22.96%, Mn:19.85%, Fe:4.04%, Zn:12.28%, Cr:0.75%, Zr:39.55%, K:0.57%.The CO hydrogenation reaction is carried out at continuous fixed bed reactor, loaded catalyst 2mL, before reaction first with synthesis gas the lower reduction of normal pressure, 300 ℃ 12 hours, be down to and transfer to appropraite condition after the room temperature and react.Service condition is: T=240 ℃, and p=6.0MPa, GHSV=5000h
-1, H
2/ CO(mol ratio)=1.The product chromatography of after refrigerated separation, taking a sample, the result is as follows:
Embodiment 7
Take by weighing respectively cycloheptane 150g, Triton X-100 (Triton X-100) 75g, Decanol 75g stirs the formation oil-phase solution; Other takes off the row metal nitrate by mole% Cu 25%, Mn 18%, Fe 5%, Zn 20%, Cr 1%, and Zr 30% is dissolved in that to form concentration with the isopyknic distilled water of mentioned solution be the mixed solution of 0.3mol/L, and this solution is dropped to above-mentioned oil-phase solution by the speed of 10mL/min, stir while dripping, be made into microemulsion system.Other gets potash and is mixed with 30% solution, drop to above-mentioned microemulsion system to pH value and be till 9.0, react complete after with this mixed solution at 45 ℃ of aging 4h, behind the 3000r/min centrifugation 10min, remove the upper strata stillness of night,, to the obvious oil phase of sediment surface nothing and surfactant, be washed with distilled water to till the neutrality again with absolute ethanol washing.With the 1%(molar percentage) be dissolved in distilled water (with the sediment equal-volume), add the sediment of above-mentioned gained and stir the formation pastel, 400 ℃ of roasting 2h estimate after compressing tablet sieves after 120 ℃ of dryings.Each weight metal percentage composition is Cu:22.72%, Mn:14.14%, Fe:3.99%, Zn:18.70%, Cr:0.75%, Zr:39.14%, K:0.56%.The CO hydrogenation reaction is carried out at continuous fixed bed reactor, loaded catalyst 2mL, before reaction first with synthesis gas the lower reduction of normal pressure, 300 ℃ 12 hours, be down to and transfer to appropraite condition after the room temperature and react.Service condition is: T=240 ℃, and p=6.0MPa, GHSV=4000h
-1, H
2/ CO(mol ratio)=2.0.The product chromatography of after refrigerated separation, taking a sample, the result is as follows:
Claims (7)
1. the copper-based catalysts of a synthesizing low-carbon mixed alcohol is characterized in that the catalyst molar percentage consists of:
Cu：25-40%，Mn：25-40%，Fe：1-10%，?Zn：5-20%，
Cr：0.5-5%，Zr：10-30%，K：0.05-2%。
2. the preparation method of the copper-based catalysts of a kind of synthesizing low-carbon mixed alcohol as claimed in claim 1 is characterized in that may further comprise the steps:
(1) with the in mass ratio ratio mixing of 2～4:1:1～0.5 of surfactant, cosurfactant and oil phase, the formation oil-phase solution stirs;
(2) nitrate of getting in addition Cu, Mn, Fe, Zn, Cr, Zr is dissolved in the isopyknic distilled water of mentioned solution to form mixed solution, the speed of this solution by 2～20mL/min is dropped in step (1) oil-phase solution, stir while dripping, be made into microemulsion system;
(3) then the alkaline solution of preparation 0.1-1.0mol/L drops to above-mentioned microemulsion system to pH value and is till 7～10;
(4) step (3) gains are lower aging 1-24 hour at 25-80 ℃, after the 1000-5000r/min centrifuge separates 5-30min, to the obvious oil phase of sediment surface nothing and surfactant, be washed with distilled water to again till the neutrality with absolute ethanol washing;
(5) potash is dissolved in the isopyknic distilled water of step (4) sediment after, add the sediment of step (4) gained, and stir into pastel, after 40-150 ℃ of drying 300-550 ℃ roasting 1-6 hour, obtain catalyst after compressing tablet sieves.
3. the preparation method of the copper-based catalysts of a kind of synthesizing low-carbon mixed alcohol as claimed in claim 1, it is characterized in that described surfactant is softex kw, dioctadecyl dimethyl ammonium chloride, Triton X-100, dioctyl sodium sulfosuccinate, dodecyl sodium sulfate, a kind of in neopelex or the lauryl alcohol polyoxyethylene sodium sulphate.
4. the preparation method of the copper-based catalysts of a kind of synthesizing low-carbon mixed alcohol as claimed in claim 1 is characterized in that described cosurfactant is a kind of in n-butanol, n-amyl alcohol, n-hexyl alcohol, n-heptanol, n-octyl alcohol, Decanol or the n-dodecanol.
5. the preparation method of the copper-based catalysts of a kind of synthesizing low-carbon mixed alcohol as claimed in claim 1 is characterized in that described oil phase is a kind of in hexane, heptane, octane, cyclohexane, cycloheptane or the cyclooctane.
6. the preparation method of the copper-based catalysts of a kind of synthesizing low-carbon mixed alcohol as claimed in claim 1 is characterized in that described alkaline solution is a kind of in sodium carbonate, potash or the ammoniacal liquor.
7. the application of the copper-based catalysts of a kind of synthesizing low-carbon mixed alcohol as claimed in claim 1, it is characterized in that application conditions is: reaction temperature is 200-300 ℃, and pressure is 2.0-8.0MPa, and gas space velocity is 500-10000h
-1, H
2The mol ratio of/CO is 0.5-3.0.
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