CN103657657B - A kind of oxygenatedchemicals hydrogenation catalyst and preparation method thereof - Google Patents
A kind of oxygenatedchemicals hydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN103657657B CN103657657B CN201210320374.2A CN201210320374A CN103657657B CN 103657657 B CN103657657 B CN 103657657B CN 201210320374 A CN201210320374 A CN 201210320374A CN 103657657 B CN103657657 B CN 103657657B
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Abstract
A kind of oxygenatedchemicals hydrogenation catalyst, comprises alumina support and with the following active component of the butt carrier content that is benchmark: boron oxide 1 ~ 25 quality %, zinc oxide 2 ~ 30 quality %, copper 2 ~ 16 quality %.This catalyst is used for the hydrogenation reaction of the oxygenatedchemicals such as ester, acid, alcohol, can improve hydrogenating materials conversion ratio.
Description
Technical field
The present invention is a kind of oxygenatedchemicals hydrogenation catalyst and preparation method thereof, specifically, is a kind of Catalysts and its preparation method of cupric-zinc.
Background technology
The large-scale production of biodiesel causes by-product glycerin excess production capacity.Utilizing this type of glycerine resource, by the 1,2-PD of catalytic hydrogenation production high added value, is the important research direction of biological support diesel oil industry development.The major product fatty acid methyl ester of biodiesel also can be used for the higher alcohols of production high added value in addition, and the technology developing new fatty acid methyl ester production higher alcohols becomes problem demanding prompt solution.
CN200610105255.X discloses a kind of method of preparing 1,2-dihydroxypropane by glycerine hydrogenation, adopts CuO-SiO
2catalyst, wherein containing the CuO of 30 ~ 65 quality %, this catalyst needs reduction before use, and for glycerine hydrogenation, when compounding high concentration glycerite, glycerol conversion yield is lower.
USP5214219 discloses the technique of a kind of preparing 1,2-dihydroxypropane by glycerine hydrogenation and ethylene glycol, and this technique adopts CuO, ZnO and Al
2o
3for catalyst, reaction pressure 5 ~ 20MPa, when glycerol conversion yield is 93.2%, the most high selectivity of 1,2-PD reaches 94%, but this result obtains under the pressure of 15MPa.
CN200710020031.3 discloses a kind of glycerin catalytic hydrogenation continuous production 1, the method of 2-propane diols, the method uses the catalyst containing copper and zinc and manganese/or aluminium, glycerin catalytic hydrogenation reaction is carried out under temperature 200 ~ 250 DEG C, pressure 2.5 ~ 5.0MPa, 1,2-propane diols is selective reaches 95 quality %, but low conversion rate is in 95%.
CN200810034426.3 discloses a kind of Cu-Zr-A catalyst, and A is wherein selected from titanium, tungsten or molybdenum, at temperature 220 DEG C, pressure 6.0MPa, air speed 0.5h
-1condition under, glycerol conversion yield can reach 99%, and 1,2-PD is selective is 95%, but its metal adopted is more expensive, and H
2/ glycerine mol ratio is higher, is 50.
CN101816936 discloses a kind of Cu-A-Al catalyst, and wherein A is one or more in Ni, Zn, Sn, Co, Fe, Mn, Ti, W, but the glycerol conversion yield of this catalyst and 1,2-PD is selective not high.
CN102040477A discloses a kind of method of preparing 1,2-dihydroxypropane by glycerine hydrogenation, and use copper zinc-aluminium carbon multicomponent composite catalyst, the glycerol conversion yield of this catalyst can reach more than 90%, but propane diols is selective lower than 90%.
CN101298052A discloses a kind of copper zinc catalyst, and this catalyst adopts mesoporous molecular sieve, a certain amount of copper of load and zinc, and the conversion ratio that this catalyst is used for fatty acid methyl ester hydrogenation is slightly low.
USP5120700 discloses a kind of copper-iron-aluminium-zinc catalyst, prepare higher alcohols, but reaction pressure is higher for fatty acid methyl ester hydrogenation.
USP5124491 discloses a kind of copper-chromium-magnesium-silicon-titanate catalyst, and it is active that this catalyst has higher fatty acid methyl ester hydrogenation, but selective lower.
The people such as ChenYZ (CatalysisLetters, 1997,48:101-104) disclose a kind of Cu-B
2o
3/ SiO
2catalyst, produce higher alcohols, but effect is not satisfactory for fatty acid methyl ester batch (-type) hydrogenation.
Summary of the invention
The object of this invention is to provide a kind of oxygenatedchemicals hydrogenation catalyst and preparation method thereof, this catalyst is used for the hydrogenation reaction of the oxygenatedchemicals such as ester, acid, alcohol, can improve hydrogenating materials conversion ratio.
Oxygenatedchemicals hydrogenation catalyst provided by the invention, comprises alumina support and with the following active component of the butt carrier content that is benchmark:
Boron oxide 1 ~ 25 quality %,
Zinc oxide 2 ~ 30 quality %,
Copper 2 ~ 16 quality %.
The present invention is load amount of copper-zinc-boron in alumina support, effectively can improve the activity of catalyst for oxygenatedchemicals hydrogenation reaction, and increase the life-span of catalyst, and hydrogenation conditions is gentle.
Detailed description of the invention
The present invention take aluminium oxide as carrier, in copper-zinc component, add boron oxide, and the hydrogenation reaction that effectively can improve catalyst is active, and keeps higher object selectivity of product, and catalyst life also increases.
The present invention take aluminium oxide as carrier, load active component boron oxide, zinc oxide and copper, active component content take carrier as benchmark, and the content of preferred active component is: boron oxide 3 ~ 20 quality %, more preferably 4 ~ 15 quality %, zinc oxide 6 ~ 20 quality %, copper 4 ~ 12 quality %.
The preferred 1:1.5 of the mol ratio of institute's cupric and zinc in described catalyst.
The preferred gama-alumina of described aluminium oxide, its specific area is 180 ~ 400m
2/ g, preferably 240 ~ 350m
2/ g, pore volume is 0.2 ~ 0.8cm
3/ g, preferably 0.3 ~ 0.6cm
3/ g.
Catalyst of the present invention adopts infusion process to introduce active component, and co-impregnation can be adopted to introduce active component simultaneously, and preferably substep introduces active component.When substep introduces active component, preferably in the end a step introduces copper.The preferred preparation method of the present invention has following two kinds.
A kind of preferred preparation method of catalyst of the present invention comprises the aqueous impregnation by alumina support boron-containing compound and zinc compound, after dipping after solid drying, roasting, then uses the aqueous impregnation of copper-containing compound, uses hydrogen reducing after drying, roasting.
The another kind of preferred preparation method of catalyst of the present invention comprises the aqueous impregnation of alumina support boron-containing compound, the aqueous impregnation of zinc compound is used again after drying, roasting, dry, roasting, then uses the aqueous impregnation of copper-containing compound, uses hydrogen reducing after drying, roasting.
In said method, described boron-containing compound preferred boric acid.The preferred zinc nitrate of described zinc compound, zinc acetate or zinc sulfate.The preferred copper nitrate of described copper-containing compound, copper sulphate or copper acetate.
In said method, the temperature that dipping introduces active component is 0 ~ 99 DEG C, preferably 10 ~ 30 DEG C.After dipping, the baking temperature of solid is 80 ~ 120 DEG C, and drying time is 4 ~ 24h preferably, and sintering temperature is 400 ~ 600 DEG C, preferably 450 ~ 550 DEG C, and roasting time is 4 ~ 8h preferably.
After said method introduces active component in the carrier, drying, roasting obtain catalyst, and copper wherein exists with oxidation state, then become metallic state with hydrogen reducing.Be 200 ~ 450 DEG C, preferably 250 ~ 400 DEG C by the temperature of hydrogen reducing, the recovery time is 4 ~ 8h preferably.
The preparation method of catalyst carrier of the present invention is: by aluminium oxide or its precursor water, after preferably using peptizing agent to mediate, and extruded moulding, and then dry, roasting.Described peptizing agent is inorganic acid and/or the organic acid aqueous solution, and concentration is 1 ~ 10 quality % preferably, the preferred nitric acid of described inorganic acid, the preferred acetic acid of organic acid or citric acid.Described aluminium oxide precursor is aluminium hydroxide or boehmite.Described baking temperature is 90 ~ 120 DEG C, sintering temperature is 450 ~ 700 DEG C, preferably 480 ~ 650 DEG C.
Be suitable for the oxygenatedchemicals that catalyst of the present invention carries out hydrogenation reaction and comprise ester, organic acid or alcohol, preferably glycerine, fatty acid methyl ester, the carbon number of described fatty acid methyl ester is 10 ~ 24, preferably 13 ~ 20, preferred methyl hexadecanoate or methyl linolenate.
Catalyst of the present invention be used for the reaction condition of glycerine hydrogenation 1,2-PD be temperature 160 ~ 280 DEG C, preferably 220 ~ 260 DEG C, pressure 1.0 ~ 8.0MPa, preferably 2.0 ~ 6.0MPa, material quality air speed is 0.2 ~ 3.0h
-1, preferred 0.5 ~ 2h
-1, the mol ratio of hydrogen/glycerine is 1 ~ 12, preferably 2 ~ 8.When carrying out hydrogenation to glycerine, preferably glycerine and methyl alcohol being mixed and made into glycerol content is that the glycerine methanol solution of 30 ~ 80 quality %, preferably 60 ~ 80 quality % is as raw material.
The reaction temperature that catalyst of the present invention is used for fatty acid methyl ester hydrogenation high-carbon fatty alcohol is 180 ~ 300 DEG C, preferably 220 ~ 280 DEG C, and pressure is 4.0 ~ 12.0MPa, preferably 7.0 ~ 10.0MPa, and material quality air speed is 1 ~ 10h
-1, preferred 2 ~ 6h
-1, the mol ratio of hydrogen/fatty acid methyl ester is 1 ~ 10, preferably 2 ~ 8.When carrying out hydrogenation to fatty acid methyl ester, preferably by fatty acid methyl ester and C
5~ C
6alkane to be mixed and made into fatty acid methyl ester be that the alkane solution of 5 ~ 30 quality %, the preferably fatty acid methyl ester of 5 ~ 15 quality % is as raw material.Described C
5~ C
6the preferred pentane of alkane and/or isopentane.
Below by example in detail the present invention, but the present invention is not limited to this.
Example 1
Prepare the carrier that catalyst of the present invention is used.
Get the aluminium hydroxide that 500 grams of Wenzhou alumina producers are produced, add the salpeter solution that 350ml concentration is 5 quality %, mediate evenly, extruded moulding, 120 DEG C of dryings 4 hours, are cut into the particle of length 1 ~ 2mm, 500 DEG C of roastings 4 hours, obtain gamma-aluminium oxide carrier, its specific area is 294m
2/ g, pore volume are 0.36cm
3/ g.
Example 2
Prepare catalyst of the present invention.
(1) in carrier, boron oxide is introduced
Get gamma-aluminium oxide carrier prepared by 10g example 1,3.6g boric acid is dissolved in 12g water and makes maceration extract, with maceration extract in 20 DEG C of above-mentioned carrier 24h of dipping, 100 DEG C of dry 12h, 540 DEG C of roasting 4h.
(2) in carrier, zinc and copper is introduced
0.6g copper nitrate and 1.1g zinc nitrate are dissolved in 10g water and make maceration extract, with the carrier 12 h of maceration extract after 20 DEG C of dipping (1) one-step bakings, 120 DEG C of dry 8h, 500 DEG C of roasting 8h, use hydrogen in 300 DEG C of reduction 6h again, obtained catalyst A is wherein that the active component content of benchmark is with gamma-aluminium oxide carrier: boron oxide 20 quality %, zinc oxide 3 quality %, copper 1.6 quality %.
Example 3
(1) in carrier, boron oxide and zinc oxide is introduced
Get gamma-aluminium oxide carrier prepared by 10g example 1,1.8g boric acid and 6.08g zinc acetate are dissolved in 20g water and make maceration extract, with maceration extract in 20 DEG C of dippings above-mentioned carrier 36h, 80 DEG C of dry 24h, 500 DEG C of roasting 8h.
(2) in carrier, copper is introduced
3.75g copper acetate is dissolved in 12g water and makes maceration extract, with the carrier 24h of maceration extract after 25 DEG C of dipping (1) one-step bakings, 100 DEG C of dry 12h, 500 DEG C of roasting 6h, use hydrogen in 400 DEG C of reduction 6h again, obtained catalyst B is wherein that the active component content of benchmark is with gamma-aluminium oxide carrier: boron oxide 10 quality %, zinc oxide 22.5 quality %, copper 12 quality %.
Example 4
(1) in carrier, boron oxide and zinc oxide is introduced respectively
Get gamma-aluminium oxide carrier prepared by 10g example 1,2.7g boric acid is dissolved in 15g water and makes maceration extract, with maceration extract in 25 DEG C of above-mentioned carrier 12 h of dipping, 120 DEG C of dry 12h, 500 DEG C of roasting 4h.Again 5.5g zinc nitrate is dissolved in 12g water, boracic carrier obtained after adding roasting, in 25 DEG C of dipping 24h, 100 DEG C of dry 12h, 500 DEG C of roasting 8h.
(2) in carrier, copper is introduced
3g copper nitrate is dissolved in 12g water and makes maceration extract, with the carrier 24h that maceration extract is prepared in 25 DEG C of dipping (1) steps, 100 DEG C of dry 12h, 500 DEG C of roasting 6h, use hydrogen in 360 DEG C of reduction 8h again, obtained catalyst C is wherein that the active component content of benchmark is with gamma-aluminium oxide carrier: boron oxide 15 quality %, zinc oxide 15 quality %, copper 8 quality %.
Example 5
(1) in carrier, boron oxide and zinc oxide is introduced
Get gamma-aluminium oxide carrier prepared by 10g example 1,0.18g boric acid and 6.1g zinc acetate are dissolved in 15g water and make maceration extract, with maceration extract in 15 DEG C of above-mentioned carrier 24h of dipping, 80 DEG C of dry 24h, 500 DEG C of roasting 8h.
(2) in carrier, copper is introduced
4.5g copper nitrate is dissolved in 12g water and makes maceration extract, with the carrier 24h of maceration extract after 15 DEG C of dipping (1) one-step bakings, 100 DEG C of dry 12h, 500 DEG C of roasting 6h, use hydrogen in 400 DEG C of reduction 6h again, obtained catalyst D is wherein that the active component content of benchmark is with gamma-aluminium oxide carrier: boron oxide 1 quality %, zinc oxide 22.5 quality %, copper 12 quality %.
Example 6
(1) in carrier, boron oxide and zinc oxide is introduced respectively
Get gamma-aluminium oxide carrier prepared by 10g example 1,0.9g boric acid is dissolved in 10g water and makes maceration extract, with maceration extract in 30 DEG C of above-mentioned carrier 12 h of dipping, 120 DEG C of dry 12h, 500 DEG C of roasting 4h.Again 3.3g zinc nitrate is dissolved in 12g water, boracic carrier obtained after adding roasting, in 30 DEG C of dipping 24h, 100 DEG C of dry 12h, 500 DEG C of roasting 8h.
(2) in carrier, copper is introduced
1.8g copper nitrate is dissolved in 10g water and makes maceration extract, with the carrier 12 h that maceration extract is prepared in 30 DEG C of dipping (1) steps, 100 DEG C of dry 12h, 500 DEG C of roasting 6h, use hydrogen in 450 DEG C of reduction 8h again, obtained catalyst E is wherein that the active component content of benchmark is with gamma-aluminium oxide carrier: boron oxide 5 quality %, zinc oxide 9 quality %, copper 4.8 quality %.
Example 7
(1) in carrier, boron oxide and zinc oxide is introduced
Get gamma-aluminium oxide carrier prepared by 10g example 1,1.8g boric acid and 6.6g zinc nitrate are dissolved in 15g water and make maceration extract, with maceration extract in 15 DEG C of above-mentioned carrier 36h of dipping, 80 DEG C of dry 24h, 500 DEG C of roasting 8h.
(2) in carrier, copper is introduced
3.6g copper nitrate is dissolved in 12g water and makes maceration extract, with the carrier 24h of maceration extract after 15 DEG C of dipping (1) one-step bakings, 100 DEG C of dry 12h, 500 DEG C of roasting 6h, use hydrogen in 400 DEG C of reduction 6h again, obtained catalyst F is wherein that the active component content of benchmark is with gamma-aluminium oxide carrier: boron oxide 10 quality %, zinc oxide 18 quality %, copper 9.6 quality %.
Comparative example 1
Prepare copper-zinc catalyst
(1) in carrier, zinc oxide is introduced
Get gamma-aluminium oxide carrier prepared by 10g example 1,3.3g zinc nitrate is dissolved in 12g water and makes maceration extract, with maceration extract in 30 DEG C of above-mentioned carrier 24h of dipping, 100 DEG C of dry 12h, 500 DEG C of roasting 8h.
(2) in carrier, copper is introduced
1.8g copper nitrate is dissolved in 10g water and makes maceration extract, with the carrier 12 h of maceration extract after 30 DEG C of dipping (1) one-step bakings, 100 DEG C of dry 12h, 500 DEG C of roasting 6h, use hydrogen in 450 DEG C of reduction 8h again, obtained catalyst G is wherein that the active component content of benchmark is with gamma-aluminium oxide carrier: zinc oxide 9 quality %, copper 4.8 quality %.
Comparative example 2
The C3-XH-3 type Cu-Cr catalyst produced with Xin Jida Chemical Co., Ltd. of Taiyuan City is for comparative catalyst, and be designated as catalyst H, wherein the mol ratio of chromium and copper is 1:1, and containing a small amount of Ba, specific area is 73m
2/ g, pore volume are 0.17cm
3/ g.
Example 8 ~ 15
Following instance investigates the performance that catalyst of the present invention reacts for glycerine hydrogenation.
Glycerine and methyl alcohol are pressed the mass ratio mixing of 7:3 as reaction raw materials, at 240 DEG C, 4.0MPa, material quality air speed is 1.0h
-1, H
2/ glycerine mol ratio is under the reaction condition of 3.0, and investigate the glycerine hydrogenation performance of catalyst, the results are shown in Table 1, in table 1, the not marked reaction time is 4h.
As seen from the results in Table 1, catalyst of the present invention, than comparative catalyst, has higher glycerol conversion yield, and catalyst activity stability is better, and it is still higher to react glycerol conversion yield after 24 hours.
Example 16 ~ 23
Following instance investigates the performance that catalyst of the present invention reacts for fatty acid methyl ester hydrogenation.
Methyl hexadecanoate is mixed as raw material with pentane by the mass ratio of 10:90,250 DEG C, 8.0MPa, material quality air speed be 4.0h
-1, hydrogen/methyl hexadecanoate mol ratio 5.0 reaction condition under, investigate catalyst to the hydrogenation reaction performance of methyl hexadecanoate, the results are shown in Table 2, in table 2, the not marked reaction time is 4h.
As seen from the results in Table 2, catalyst of the present invention, than comparative catalyst, has higher methyl hexadecanoate conversion ratio, and catalyst activity stability is better, react 24 hours substantially suitable with the methyl hexadecanoate conversion ratio reacting 4 hours.
Table 1
Table 2
Claims (6)
1. an oxygenatedchemicals hydrogenation catalyst, comprises alumina support and with the following active component of the butt carrier content that is benchmark:
Boron oxide 3 ~ 20 quality %,
Zinc oxide 6 ~ 20 quality %,
Copper 4 ~ 12 quality %,
Described alumina support is gama-alumina, and its specific area is 180 ~ 400m
2/ g, pore volume are 0.2 ~ 0.8cm
3/ g,
The preparation method of described catalyst, comprises the aqueous impregnation by alumina support boric acid and zinc compound, after dipping after solid drying, roasting, then uses the aqueous impregnation of copper-containing compound, with hydrogen reducing after drying, roasting, or
Comprise the aqueous impregnation of alumina support boric acid, use the aqueous impregnation of zinc compound after drying, roasting again, dry, roasting, then uses the aqueous impregnation of copper-containing compound, uses hydrogen reducing after drying, roasting.
2., according to catalyst according to claim 1, it is characterized in that the mol ratio of institute's cupric and zinc in described catalyst is 1:1.5.
3., according to catalyst according to claim 1, it is characterized in that described zinc compound is zinc nitrate, zinc acetate or zinc sulfate.
4., according to catalyst according to claim 1, it is characterized in that described copper-containing compound is copper nitrate, copper sulphate or copper acetate.
5., according to catalyst according to claim 1, it is characterized in that baking temperature is 80 ~ 120 DEG C, sintering temperature is 400 ~ 600 DEG C.
6., according to catalyst according to claim 1, it is characterized in that by the temperature of hydrogen reducing be 200 ~ 450 DEG C.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4386017A (en) * | 1979-11-12 | 1983-05-31 | Mitsubishi Gas Chemical Company | Preparation of improved catalyst composition |
| CN1683076A (en) * | 2004-04-16 | 2005-10-19 | 中国石油化工股份有限公司 | Catalyst for preparing dimethyl ether from synthetic gas by one step |
| CN102380389A (en) * | 2011-09-09 | 2012-03-21 | 上海戊正工程技术有限公司 | Catalyst for preparation of 1,6-hexanediol by hydrogenating 1,6-hexanedioic acid dialkyl ester and preparation method and application thereof |
| CN103170338A (en) * | 2011-12-23 | 2013-06-26 | 北京石油化工学院 | Catalyst for 1,2-propylene glycol and preparation method of catalyst |
-
2012
- 2012-08-31 CN CN201210320374.2A patent/CN103657657B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4386017A (en) * | 1979-11-12 | 1983-05-31 | Mitsubishi Gas Chemical Company | Preparation of improved catalyst composition |
| CN1683076A (en) * | 2004-04-16 | 2005-10-19 | 中国石油化工股份有限公司 | Catalyst for preparing dimethyl ether from synthetic gas by one step |
| CN102380389A (en) * | 2011-09-09 | 2012-03-21 | 上海戊正工程技术有限公司 | Catalyst for preparation of 1,6-hexanediol by hydrogenating 1,6-hexanedioic acid dialkyl ester and preparation method and application thereof |
| CN103170338A (en) * | 2011-12-23 | 2013-06-26 | 北京石油化工学院 | Catalyst for 1,2-propylene glycol and preparation method of catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 甘油氢解制备丙二醇催化剂研究进展;陈忠等;《化工进展》;20111231;第30卷(第5期);第997-1002页 * |
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