CN1698955A - Catalyst for copper base hydrogenation reaction using paligorskite as supporter and method for preparing the same - Google Patents
Catalyst for copper base hydrogenation reaction using paligorskite as supporter and method for preparing the same Download PDFInfo
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- CN1698955A CN1698955A CN 200510049629 CN200510049629A CN1698955A CN 1698955 A CN1698955 A CN 1698955A CN 200510049629 CN200510049629 CN 200510049629 CN 200510049629 A CN200510049629 A CN 200510049629A CN 1698955 A CN1698955 A CN 1698955A
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- palygorskite
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Abstract
This invention discloses a copper based hydrogenation reaction catalyst using paligorskite as the carrier, in addition to its preparing method. The percentage by weight of elements is: copper 5~20%, iron family elements 5~10%. The preparing method comprises the following steps: implanting the concerned elements into paligorskite lattice through ion displacement reaction; deacidizing copper and iron family elements which are distributed in the paligorskite surface and tunnel surface to the metal particles, wherein the catalyst is distributed evenly in the carrier and connects fast to the carrier. Said catalyst is fit for kinds of hydrogenation reaction in the chemical and chemical industry fields, especially for catalyzing in reaction of compounding fuel low-carbon alcohol with water-gas.
Description
Technical field
The present invention relates to chemistry or physical method, relating in particular to a kind of is the catalyst for copper base hydrogenation reaction and preparation method thereof of carrier with the palygorskite.
Background technology
Copper-based catalysts has been widely used in the catalysis of hydrogenation, especially the hydrogenation reaction of catalysis carbon monoxide and carbon dioxide.Carbon monoxide, carbon dioxide and hydrogen are the main components of water-gas, and under certain condition, copper-based catalysts can cause hydrogenation in water-gas, obtain low-carbon alcohols, thereby make coal change into liquid fuel through water-gas.The shortage of petroleum resources is problems that China must face, and too relies on the energy security that the international market will have a strong impact on country.It is in short supply to use catalyst for copper base hydrogenation reaction to realize that water-gas can be alleviated fuel oil to a certain extent to the conversion of fuel alcohol.
The general oxide that manually synthesizes that uses of existing copper-based catalysts is as Al
2O
3, SiO
2And ZrO
2In the carrier as copper, they exist carrier to combine not good enough, metal defective such as skewness on carrier with metal particle in varying degrees, and expensive as the oxide fine particle of carrier.Development of new catalyst and catalyst carrier are significant for the development of hydrocracking and hydrogenation preparing industry.
Summary of the invention
The purpose of this invention is to provide a kind of is the catalyst for copper base hydrogenation reaction and preparation method thereof of carrier with the palygorskite.
With the palygorskite is the catalyst for copper base hydrogenation reaction of carrier: in the mineral lattice of palygorskite and surperficial appendix the cation and the metal particle of copper and iron family element are arranged, by weight percentage, the content of copper in catalyst is 5～20%, and the content of iron family element in catalyst is 5～10%.
Said palygorskite is a kind of magnesium silicate mineral with layer chain structure, and its theoretical molecular formula is:
Mg
5Si
8O
20(OH)
2(OH
2)
4·4H
2O
It is clay, mud stone, shale or loose massive ore in natural output form.Said iron family element is a kind of among Fe, Co, Zn, Mn, Cr, the V or several.
The preparation method who with the palygorskite is the catalyst for copper base hydrogenation reaction of carrier may further comprise the steps:
1) through separate purifying, and to be crushed to less than 300 purpose palygorskites and weight be that 3～8 times acid solution mixes, and stirs, reacted 30～50 hours, continue to stir during this time, centrifugal then or filtering means dehydration, water cleaning～dehydration 3～5 times is to remove remaining acid solution;
2) mixture dehydration back and weight are that the polybasic salt solution of 4～6 times in ore is evenly mixed, react 30～60 hours, during stir for several times, in stirring, slowly add concentration then and be 0.5～5 mole NaOH or ammonia spirit, make the pH of mixed value be not less than 6;
3) mixed liquor is filtered or centrifugal dehydration, water cleans 2～3 times, again spray-drying after the slurrying;
4) the gained powder was handled 2～4 hours in 400～500 ℃ nitrogen stream, added 3～10% hydrogen then in nitrogen stream, continue to handle 2～5 hours, and cool to room temperature in nitrogen stream, products therefrom is hydrogenation catalyst.
Said acid solution is that concentration is 3～5 moles hydrochloric acid, nitric acid or sulfuric acid.
Said polybasic salt solution be contain 1～4 mole mantoquita and and the mixed solution of 1～2 mole of iron group salt; Mantoquita is a kind of in hydrochloric acid copper, copper nitrate, copper sulphate and the hydrate thereof or several; Iron group salt is a kind of in iron family element hydrochloride, iron family element nitrate, iron family element sulfate and the hydrate thereof or several.
It is the carrier of copper-based catalysts that the present invention adopts natural slope thread masonry, and it has wide material sources, cheap advantage.On the preparation method, the present invention adopts the selectivity corrosion to remove the cation of palygorskite lattice octahedral site, by the ion exchange reaction copper and iron family element are implanted the palygorskite lattice, in containing the reproducibility air-flow of hydrogen, the copper and the iron family element on mineral surfaces and hole path surface, intracrystalline tunnel are reduced into metal particle, therefore catalyst is evenly distributed on carrier, combine with carrier very firm, so its service life and catalytic activity all will to be higher than be the copper-based catalysts of carrier traditionally with the oxide.
The present invention proposes is all kinds of hydrogenation reactions that the catalyst for copper base hydrogenation reaction of carrier is applicable to chemistry, chemical field with the palygorskite, the hydrogenation that is particularly useful for catalysis carbon monoxide and carbon dioxide, and catalysis is the reaction of raw material synthetic fuel alcohol with water-gas.
The specific embodiment
Palygorskite is a kind of natural magnesium silicate mineral with chain layer structure.The outer formation of palygorskite is fibrous, diameter 10～100 nanometers, and several microns to tens microns of length, from the monocrystalline size, it meets the definition of nano material, belongs to typical natural 1-dimention nano mineral.
The theoretical molecular formula of palygorskite is:
Mg
5Si
8O
20(OH)
2(OH
2)
44H
2O accompanies a Mg-O (OH) octahedral layer between per two Si-O tetrahedral layers on crystalline texture, form basic structural unit, and basic structural unit is staggered, and has formed the hole, tunnel that is parallel to lattice direction, and its cross section is 0.37 * 0.64 nanometer.The hole, intracrystalline tunnel of nano-scale makes palygorskite have huge specific area and absorption～catalytic activity, and this is the basis that it is suitable for being used as catalyst carrier.
Palygorskite is general and impure mineral symbiosis at nature, and tight agglomeration each other, output form are clay, mud stone, shale or the massive ore that loosens.Use known technology to separate the natural palygorskite (having another name called attapulgite) of purifying among the present invention, it comprises that pulverizings, making beating make suspension, classification collection less than the particle of 5 μ etc.This palygorskite through purifying is the clay mineral of a kind of light gray, light green color tool layered crystal structure.Separate purification process and can select conventional mining equiment for use.
Preparation method's the first step is to be crushed to less than 300 purpose palygorskite and acid solution reactions, can to use hydrochloric acid, nitric acid or sulfuric acid, to take all factors into consideration from environment and cost factor, recommends to use hydrochloric acid.Impure mineral remaining in the ore can be dissolved by acid, as carbonate, partial clay mineral, iron and manganese oxides and silicate hydroxide minerals.Should adjust the concentration and the consumption of acid during practical operation according to composition of ores, the ore that the solubility in acid impurity content is high can improve the concentration of acid or increase with the acid amount.In the acid treatment process, the cation of octahedral site in the palygorskite lattice (refers to remove Si
4+Other cation in addition) tend to by the selectivity corrosion, these cationic lattice positions are by H
+Ion replaces.Mixture can be heated to 60～90 ℃ in the molten process of acid, so that accelerate reaction process.Should dewater and wash after acid is molten, remove remaining acid.
Preparation method's second step is to use the polybasic salt solution of being made up of mantoquita and iron group salt that palygorskite is carried out ion exchange.After palygorskite and the polynary salt solution mix, the cation in the solution enters the octahedral site of mineral lattice, makes palygorskite recover the molten preceding structure of acid.Iron family element refers to a kind of in No. 23 to No. 27 elements and No. 30 elements or several.Anion in the salt is little to ion exchange reaction influence, can be whether according to the facility of raw material sources, and price factor is selected suitable salt.With NaOH or ammoniacal liquor solution being neutralized after the ion exchange is in order to make copper remaining in the solution and the iron group cation form precipitation with hydroxide, to improve its utilization rate and to reduce discharging.Should dewater and wash after the neutralization, to remove formed sodium salt or ammonia salt.
Before spray-drying, need ore pulp slurrying again to having dewatered, should grasp amount of water this moment, and ore pulp is feeding-up then mobile poor, crosses rare spray-dired energy consumption that then increased.The spray-drying product is loosely organized microballoon under electron microscope, has very high surface-active, and is favourable to next step reduction reaction.
In 400～500 ℃ nitrogen stream, carry out preliminary treatment before the hydro-reduction, to remove zeolite water and the constitution water in the palygorskite.Thoroughly the dehydration back adds 3～10% hydrogen in nitrogen stream, makes the copper and the iron group cation of carrier surface and intracrystalline tunnel pore surface be reduced to metal particle.In nitrogen stream, behind the cool to room temperature, product should be kept in the high pure nitrogen atmosphere, in order to avoid the moisture absorption, oxidation lose catalytic activity.
Further specify the present invention below in conjunction with instantiation.
Embodiment 1:
1) take by weighing 10 kilograms and be crushed to, add 30 kilograms of concentration and be 5 moles salpeter solution, stir, reacted 30 hours less than 300 purpose palygorskites, during continue to stir, centrifugal then or filtering means dehydration, water cleaning～dehydration 5 times is to remove remaining acid solution;
2) prepare the polybasic salt solution of copper nitrate, ferric nitrate and cobalt nitrate in advance, contain 4 molar nitric acid copper in every liter of solution, 0.5 molar nitric acid iron, 0.5 molar nitric acid cobalt and 0.5 molar nitric acid vanadium.Get 30 kilograms of polybasic salt solution that configured, evenly mixed with the palygorskite after the acid treatment, reacted 40 hours, stir during this time for several times, when stirring, slowly add concentration then and be 0.5 mole NaOH solution, with pH meter observation pH value, equal till 6 simultaneously until the pH of mixed value;
3) with the mixed liquor centrifugal dehydration, water cleans 3 times, again spray-drying after the slurrying;
4) step 3) gained powder was handled 2 hours in 500 ℃ nitrogen stream, in nitrogen stream, added 10% hydrogen then, continue to handle 2 hours;
5) cool to room temperature in nitrogen stream, products therefrom is hydrogenation catalyst, is kept in the closed container stand-by.
Embodiment 2:
1) take by weighing 10 kilograms and be crushed to, add 80 kilograms of concentration and be 3 moles hydrochloric acid solution, stir, reacted 50 hours less than 300 purpose palygorskites, during continue to stir, centrifugal then or filtering means dehydration, water cleaning～dehydration 3 times is to remove remaining acid solution;
2) prepare the polybasic salt solution of copper chloride, ferric trichloride, zinc chloride and chromium trichloride in advance, contain 2 moles of copper chlorides, 1 mole of ferric trichloride, 0.5 mole of zinc chloride and 0.5 mole of chromium trichloride in every liter of solution.Get 50 kilograms of polybasic salt solution that configured, evenly mixed with the palygorskite after the acid treatment, reacted 40 hours, stir during this time for several times, when stirring, slowly add concentration then and be 5 moles ammonia spirit, with pH meter observation pH value, equal till 6 simultaneously until the pH of mixed value;
3) with the mixed liquor centrifugal dehydration, water cleans 5 times, again spray-drying after the slurrying;
4) step 3) gained powder was handled 4 hours in 400 ℃ nitrogen stream, in nitrogen stream, added 3% hydrogen then, continue to handle 5 hours;
5) cool to room temperature in nitrogen stream, products therefrom is hydrogenation catalyst, is kept in the closed container stand-by.
Embodiment 3:
1) take by weighing 10 kilograms and be crushed to, add 50 kilograms of concentration and be 3 moles sulfuric acid solution, stir, reacted 40 hours less than 300 purpose palygorskites, during continue to stir, centrifugal then or filtering means dehydration, water cleaning～dehydration 5 times is to remove remaining acid solution;
2) prepare the polybasic salt solution of copper sulphate, cobaltous sulfate, manganese sulfate and ferrous sulfate in advance, contain 2 mol sulfuric acid copper in every liter of solution, 1 mol sulfuric acid cobalt, 0.5 mol sulfuric acid manganese and 0.5 mol sulfuric acid are ferrous.Get 50 kilograms of polybasic salt solution that configured, evenly mixed with the palygorskite after the acid treatment, reacted 60 hours, stir during this time for several times, when stirring, slowly add concentration then and be 1 mole ammonia spirit, with pH meter observation pH value, equal till 6 simultaneously until the pH of mixed value;
3) with the mixed liquor centrifugal dehydration, water cleans 4 times, again spray-drying after the slurrying;
4) step 3) gained powder was handled 3 hours in 450 ℃ nitrogen stream, in nitrogen stream, added 3% hydrogen then, continue to handle 5 hours;
5) cool to room temperature in nitrogen stream, products therefrom is hydrogenation catalyst, is kept in the closed container stand-by.
Embodiment 4:
1) take by weighing 10 kilograms and be crushed to, add 80 kilograms of concentration and be 3 moles hydrochloric acid solution, stir, reacted 50 hours less than 300 purpose palygorskites, during continue to stir, centrifugal then or filtering means dehydration, water cleaning～dehydration 5 times is to remove remaining acid solution;
2) prepare the polybasic salt solution of copper nitrate, cobalt nitrate, chromic nitrate and zinc nitrate in advance, contain 4 mol sulfuric acid copper in every liter of solution, 1 molar nitric acid cobalt, 0.5 molar nitric acid chromium and 0.5 molar nitric acid zinc.Get 30 kilograms of polybasic salt solution that configured, evenly mixed with the palygorskite after the acid treatment, reacted 60 hours, stir during this time for several times, when stirring, slowly add concentration then and be 5 moles ammonia spirit, with pH meter observation pH value, equal till 6 simultaneously until the pH of mixed value;
3) with the mixed liquor centrifugal dehydration, water cleans 3 times, again spray-drying after the slurrying;
4) step 3) gained powder was handled 2 hours in 500 ℃ nitrogen stream, in nitrogen stream, added 10% hydrogen then, continue to handle 2 hours;
5) cool to room temperature in nitrogen stream, products therefrom is hydrogenation catalyst, is kept in the closed container stand-by.
The present invention adopts separation to purify and deploymerization and decentralization technology obtains the nanometer palygorskite powder from natural crystal, adopt the ion exchange reaction that copper and iron family element are implanted the palygorskite lattice, in the reproducibility air-flow, the copper and the iron group of mineral surfaces and intracrystalline tunnel hole surface are reduced into metal particle, therefore catalyst is evenly distributed on carrier, combines very firm with carrier.Its advantage is that raw material has cost advantage from the huge natural mineral resource of reserves; It is the copper-based catalysts of carrier traditionally with the oxide that service life and catalytic activity all will be higher than; With the palygorskite all kinds of hydrogenation reactions that the catalyst for copper base hydrogenation reaction of carrier is applicable to chemistry, chemical field, being particularly suitable for catalysis is the reaction of raw material synthetic fuel low-carbon alcohols with water-gas, for realizing lique faction of coal, alleviate that fuel oil is in short supply a significant application value.
Claims (8)
1. one kind is the catalyst for copper base hydrogenation reaction of carrier with the palygorskite, it is characterized in that, in the mineral lattice of palygorskite and surperficial appendix the cation and the metal particle of copper and iron family element are arranged, by weight percentage, the content of copper in catalyst is 5～20%, and the content of iron family element in catalyst is 5～10%.
2. according to claim 1 a kind of be the catalyst for copper base hydrogenation reaction of carrier with the palygorskite, it is characterized in that said palygorskite is a kind of magnesium silicate mineral with layer chain structure, its molecular formula is:
Mg
5Si
8O
20(OH)
2(OH
2)
4·4H
2O
It is clay, mud stone, shale or massive ore in natural output form.
3. according to claim 1 a kind of be the catalyst for copper base hydrogenation reaction of carrier with the palygorskite, it is characterized in that said iron family element is a kind of among Fe, Co, Zn, Mn, Cr, the V or several.
4. one kind is the preparation method of the catalyst for copper base hydrogenation reaction of carrier with the palygorskite, it is characterized in that it may further comprise the steps:
1) through separate purifying, and to be crushed to less than 300 purpose palygorskites and weight be that 3～8 times acid solution mixes, and stirs, reacted 30～50 hours, continue to stir during this time, centrifugal then or filtering means dehydration, water cleaning～dehydration 3～5 times is to remove remaining acid solution;
2) mixture dehydration back and weight are that the polybasic salt solution of 4～6 times in ore is evenly mixed, react 30～60 hours, during stir for several times, in stirring, slowly add concentration then and be 0.5～5 mole NaOH or ammonia spirit, make the pH of mixed value be not less than 6;
3) mixed liquor is filtered or centrifugal dehydration, water cleans 2～3 times, again spray-drying after the slurrying;
4) the gained powder was handled 2～4 hours in 400～500 ℃ nitrogen stream, added 3～10% hydrogen then in nitrogen stream, continue to handle 2～5 hours, and cool to room temperature in nitrogen stream, products therefrom is hydrogenation catalyst.
5. according to claim 4 a kind of be the preparation method of the catalyst for copper base hydrogenation reaction of carrier with the palygorskite, it is characterized in that said acid solution is that concentration is 3～5 moles hydrochloric acid, nitric acid or sulfuric acid.
6. according to claim 4 a kind of be the preparation method of the catalyst for copper base hydrogenation reaction of carrier with the palygorskite, it is characterized in that containing in the said polybasic salt solution mixed solution of 1～4 mole mantoquita and 1～2 mole of iron group salt;
According to claim 4 or 6 described a kind of be the preparation method of the catalyst for copper base hydrogenation reaction of carrier with the palygorskite, it is characterized in that said mantoquita is a kind of in hydrochloric acid copper, copper nitrate, copper sulphate and the hydrate thereof or several.
8. according to claim 6 a kind of be the preparation method of the catalyst for copper base hydrogenation reaction of carrier with the palygorskite, it is characterized in that said iron group salt is a kind of in the hydrochloride of iron family element Fe, Co, Zn, Mn, Cr, V, nitrate, sulfate and the hydrate thereof or several.
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| CN 200510049629 CN1698955A (en) | 2005-04-22 | 2005-04-22 | Catalyst for copper base hydrogenation reaction using paligorskite as supporter and method for preparing the same |
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|---|---|---|---|
| CN 200510049629 CN1698955A (en) | 2005-04-22 | 2005-04-22 | Catalyst for copper base hydrogenation reaction using paligorskite as supporter and method for preparing the same |
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