CN1406666A - Catalyst for preparation of hexahydrobenzoic acid by hydrogenation of benzoic acid - Google Patents
Catalyst for preparation of hexahydrobenzoic acid by hydrogenation of benzoic acid Download PDFInfo
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- CN1406666A CN1406666A CN 01130977 CN01130977A CN1406666A CN 1406666 A CN1406666 A CN 1406666A CN 01130977 CN01130977 CN 01130977 CN 01130977 A CN01130977 A CN 01130977A CN 1406666 A CN1406666 A CN 1406666A
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Abstract
A catalyst for preparing hexahydrobenzoic acid by hydrogenating benzoic acid in fixed-bed reactor is composed of aluminium oxide as carrier and the metal in VIB or VIII family (0.1-3 wt.%). Its advantages are high activity and high purity of product (up to 75.1-79.7 wt.%).
Description
Technical field
The present invention is a kind of method of benzoic acid selective hydrogenation to prepare hexahydrobenzene formic acid, specifically, makes benzoic acid hydrogenation produce hexahydrobenzene formic acid exactly in the presence of selective hydrocatalyst.
Background technology
It is to be the intermediate reaction process that raw material is produced caprolactam with toluene that hexahydrobenzene formic acid is produced in the benzoic acid selective hydrogenation.Now the selective hydrocatalyst of Cai Yonging is a palladium/carbon catalyst, is reflected at 160～170 ℃, carries out in tank reactor under 1.2～1.4MPa condition.Because palladium/carbon catalyst is powder catalyst, with reaction raw materials and product difficulty separate.For reclaiming precious metal palladium, need palladium/carbon catalyst is thoroughly separated with other material of reaction system, therefore require the reactant benzoic acid to transform fully, to reduce the subsequent processes step.Must adopt the series connection of four stills to react, not only complex process, and product hexahydrobenzene formic acid and catalyst Long contact time also make secondary response increase for this reason, and reaction selectivity descends.Palladium/carbon catalyst loss in isolated by filtration, regeneration simultaneously is also bigger, causes the loss of precious metal palladium to increase.
Industrial noble metal with hydrogenation activity commonly used is a platinum, document ReactivePolymers, 18 (1992), 1-6 has reported that the supported method of employing organic metal prepares Pt-organic carrier catalyst, just can carry out the benzoic acid hydrogenation reaction in room temperature and produce hexahydrobenzene formic acid, and conversion ratio exists same separation, recovery and regeneration problem near 100% but this catalyst is used for industrial production.
At present, though a lot of for the report of noble metal aluminium oxide catalyst, in different applications, the character of alumina support also there is different requirements.As US4,264,529 disclose a kind of catalyst by hydrogenation of chloronitrobenzene production para-aminophenol, and it is to carry platinum by gama-alumina to make.The sintering temperature of its carrier is 500～850 ℃, and preferably 593 ℃, the specific surface of carrier is at least greater than 200 meters
2/ gram, preferably 230 meters
2/ gram.Its Pt content is 1～10%, preferred 3%.Described nitrobenzene hydrogenation needs in tank reactor and has in the presence of the water soluble acid medium to carry out, and the acid medium that uses in the example is the trimethyl ammonium chloride.
JP05,039,319 discloses a kind of adding hydrogen into resin catalyst that contains indenes, and the specific surface of its aluminium oxide is at 50～250 meters
2Between/the gram, pore volume is greater than 0.5 milliliter/gram, average pore diameter 10～28 nanometers, and Pt content is 0.5～3.0 heavy %.
US4,601,799 disclose a kind of catalyst of producing vitamin, and wherein the carrying alumina surface area per unit volume is 1～350 meter
2/ gram, the volume in the hole of bore dia in 1～60000 nanometer range are 0.35～0.60 liter/gram, and the volume in the hole of bore dia in 2～200 nanometer range accounts for 60% at least.
WO9,004,007 discloses a kind of desulphurization catalyst, and catalyst is made by oxide carried VIB or VIII family metal, and this catalyst has 5～11% macropore, and specific surface is greater than 75 meters
2/ gram.
US4,424,162 disclose a kind of Pt/ α-Al that is used for fat and vegetable oil hydrogenation
2O
3Catalyst, wherein α-Al
2O
3Specific surface is less than 15 meters
2/ gram, bore dia accounts for 90% greater than the macropore of 30 nanometers, and pore volume is less than 0.5 milliliter/gram.
DD-137806 is with a kind of Pt/Al
2O
3Catalyst is used for pyrolysis gasoline hydrogenation, and its hydrated alumina requires 450～1000 ℃ of roastings, and finished catalyst has the macropore greater than 100 nanometers, and density is low.
JP54,101,807 have invented a kind of catalyst that is used for hydrodesulfurizationof of naphtha, Tuo La and takes off aromatic hydrocarbons, and this catalyst is by VIB or VIII family metal and γ-Al
2O
3Form, the specific surface of aluminium oxide is 100～400 meters
2/ gram, bore dia is 4～20 nanometers.
US4,107,225 disclose the catalyst that a kind of polybutene hydrogenation is produced white oil, and total pore volume is greater than 0.25 milliliter/gram, and 90～98% bore dia is less than 10 nanometers, and platinum content is 0.1～1.0 heavy %.
In sum, the research and development of the catalyst of para Toluic Acid's hydrogenation preparing hexahydrobenzene formic acid are less now.Especially can adopt fixed bed reactors to carry out the research that benzoic acid hydrogenation prepares the catalyst of hexahydrobenzene formic acid does not appear in the newspapers substantially.
Summary of the invention
The purpose of this invention is to provide a kind of catalyst that is applied to the load hydrogenation active metals component of fixed bed reactors, this catalyst can make the benzoic acid selective hydrogenation produce hexahydrobenzene formic acid.
We find, alumina support load hydrogenation active metals component, when particularly the catalyst made of carried noble metal is used for the benzoic acid selective hydrogenation and produces hexahydrobenzene formic acid, carrier should have faintly acid, moderate specific area and pore volume, the size of the most of Kong Yingyu reactant molecule in the alumina support is suitable, is beneficial to benzoic benzene ring hydrogenation.
Catalyst provided by the invention is used for the benzoic acid selective hydrogenation and produces hexahydrobenzene formic acid, has high activity, high selectivity.When the catalyst that wherein carries platinum was used for fixing the bed reaction, hexahydrobenzene formic acid yield can reach 75.1～79.7 heavy %, and catalyst regeneration is more or less freely, and the loss of regenerated catalyst reduces, and the utilization rate of noble metal is improved.
The specific embodiment
Catalyst of the present invention is made up of the aluminium oxide of supported V IB or VIII family metal, and wherein tenor is 0.1～3.0 heavy %, and the specific area of alumina catalyst support is 160～210 meters
2/ gram, pore volume are that 0.5～0.6 milliliter/gram, surface acid center number are 0.2～1.5 * 10
20Individual/gram.
VIII family metal in the catalyst is selected from platinum, palladium, nickel or cobalt, preferred platinum, platinum content preferred 0.5～2.0 heavy %.The group vib metal is a molybdenum.
Preferred 170～195 meters of the specific area of described alumina catalyst support
2/ gram, the carrier average pore diameter is 7～9 nanometers, its median pore diameter be the hole of 6.0～12.0 nanometers greater than 80%, be preferably greater than 90%.Carrier surface acid site number preferred 0.7～1.3 * 10
20Individual/gram.
The used alumina support of catalyst of the present invention is to be 230～250 meters by specific area
2/ gram, the alumina hydrate powder of average pore diameter 5～7 nanometers is through extrusion molding, and 60～120 ℃ of dryings in 500～1000 ℃, made after preferred 600～950 ℃ of roastings after 4～8 hours.Therefore this alumina support has the γ crystalline phase, or the crystalline phase of mixing of γ and η, and especially when high-temperature roasting, the gained carrier contains η-Al
2O
3, therefore, the surface area of carrier is less, and pore volume is bigger.Preferred examples of the present invention be with the aluminium oxide after the moulding 850 ℃ of roastings, its surface area is 170 meters
2/ gram, pore volume are 0.52 milliliter/gram.
Described carrier extrusion molding can be used conventional method, and alumina hydrate powder and extrusion aid are mixed, and adds a certain amount of peptizing agent again, and described extrusion aid is the sesbania powder, and its dosage is 0.1～2.0% of an alumina hydrate powder weight, and preferred 0.5～1.0%.Peptizing agent can be rare nitric acid, watery hydrochloric acid, and its concentration is 2.0～10.0 heavy %.
Catalyst of the present invention is with described metal compound solution impregnated alumina preparing carriers, preferred metallic compound is a chloroplatinic acid, make maceration extract after chloroplatinic acid need being diluted with deionized water during preparation, liquid during dipping/solid volume ratio is 1.2～1.5: 1, dip time is 4～24 hours, preferred 8～20 hours, should to make the tenor of catalyst be 0.1～3.0 heavy % to the content of metallic compound in the maceration extract.Filter dipping back, 60～120 ℃ of dryings 4～8 hours, roasting in 200～550 ℃ of air then.Air mass flow is every gram catalyst 50～100 ml/min during roasting, and the time is 2～24 hours.
The comparatively preferred method of roasting of catalyst of the present invention is with the carrier behind the impregnation drying, carries out roasting in air atmosphere under three different temperature.Promptly 200～220 ℃, 350～380 ℃, 500～550 ℃ difference roasting 1～8 hour.Preferred 2～4 hours of first section roasting time, preferred 2～4 hours of second section roasting time, preferred 4～8 hours of the 3rd section roasting time.
Catalyst of the present invention before use, need 350～550 ℃ with hydrogen reducing 2～4 hours, the volume ratio of hydrogen and catalyst is 100～150: 1 during reduction, the flow of hydrogen is 100～550 milliliters/hour of every gram catalyst during reduction.
Catalyst of the present invention is applicable to the course of reaction of benzoic acid selective hydrogenation production hexahydrobenzene formic acid, and reaction can be carried out in tank reactor, also can carry out in fixed bed reactors.The reaction condition of benzoic acid selective hydrogenation is 160～220 ℃, and the hydrogen dividing potential drop is 0.5～4.0MPa, benzoic acid feed volume air speed 0.1～15.0 o'clock-1, and hydrogen hydrocarbon mol ratio is 3～15.
Further specify the present invention below by example.
Example 1
Prepare catalyst carrier of the present invention.
Take by weighing 100 gram alumina hydrate powders (German Condea company produces, and the trade mark is CI), its physico-chemical property sees Table 1.Adding 1.0 gram sesbania powder at alumina hydrate powder is mixed, add concentration again and be 50 milliliters in rare nitric acid of 3 volume %, stir to mix and pinch, be extruded into external diameter then and be 1 millimeter bar, 120 ℃ of dryings 2 hours, being cut into length is 2～3 millimeters little, 850 ℃ of roastings 4 hours, obtain carrier a, its physico-chemical property sees Table 2.Specific surface in the described physico-chemical property, pore volume adopt cryogenic nitrogen absorption BET method to measure, and the acid site number is by NH
3-TDP method is measured (referring to volumes " zeolite catalysis and isolation technics " such as height taste, P19, Sinopec publishing house).
Example 2
Method by example 1 prepares carrier e, and the sintering temperature of different is carrier is 550 ℃, and the carrier physico-chemical property sees Table 2.
Example 3
Method by example 1 prepares carrier f, and the sintering temperature of different is carrier is 950 ℃, and the carrier physico-chemical property sees Table 2.
Comparative Examples 1
Method by example 1 prepares carrier b, and different is the SB powder that the used alumina hydrate powder of preparation carrier is produced for Condea company, and its character sees Table 1, and the carrier physico-chemical property sees Table 2.
Comparative Examples 2
Method by example 1 prepares carrier c, and different is the HB powder that the used alumina hydrate powder of preparation carrier is produced for the Fushun catalyst plant, and its character sees Table 1, and the carrier physico-chemical property sees Table 2.
Comparative Examples 3
Method by example 1 prepares carrier d, and different is the SD-97 powder that the used alumina hydrate powder of preparation carrier is produced for the Zhou village catalyst plant, and its character sees Table 1, and the carrier physico-chemical property sees Table 2.
Example 4～9
Prepare catalyst of the present invention.
Get platinum content and be 8.5 milliliters of the chloroplatinic acids of 2.8 mg/ml, add deionized water and be made into 50 ml water solution.20 gram carriers are added above-mentioned solution, flooded 12 hours, 120 ℃ of dryings 2 hours, with the flow bubbling air of every gram catalyst 100 ml/min, 200 ℃ of roastings 2 hours, 380 ℃ of roastings 2 hours, 500 ℃ of roastings 4 hours.Use the nitrogen replacement air, feed hydrogen again in 500 ℃ of reduction 4 hours, hydrogen flowing quantity is every gram catalyst 5.0 ml/min, and the catalyst platinum content and the physico-chemical property that obtain see Table 3.
Example 10
Use carrier a, prepare catalyst G by the method for example 4, different is that dry rear catalyst is only 500 ℃ of roastings 6 hours.Platinum content and the physico-chemical property of catalyst G see Table 3.
Example 11
Use carrier a, prepare catalyst H by the method for example 4, the chloroplatinic acid that different add when being the preparation maceration extract is 20 milliliters, and platinum content and the physico-chemical property of catalyst H see Table 3.
Example 12
Use carrier a, prepare catalyst I by the method for example 4, the chloroplatinic acid that different add when being the preparation maceration extract is 4.0 milliliters, and the platinum content and the physico-chemical property of catalyst I see Table 3.
Example 13～21
Benzoic acid selective hydrogenation performance to catalyst of the present invention is carried out evaluation experimental.
Get 10 gram catalyst and pack in the reaction tube, in 20 milliliters of fixed-bed reactors, catalyst is carried out the hydrogenation reaction activity rating.Bed temperature is risen to 180 ℃, and it was 1.0MPa that feeding hydrogen is kept reaction pressure, with 2.0 hours
-1Mass space velocity feed benzoic acid, hydrogen and benzoic mol ratio are 5: 1, reactivity sees Table 4.
As shown in Table 4, the catalyst made of the carrier loaded platinum that makes of the hydrated alumina of selecting for use with the present invention has higher hexahydrobenzene formic acid yield than comparative catalyst B, C, D.In addition, from the response data of catalyst G also can find out preparation during catalyst through one section high-temperature roasting, its hexahydrobenzene formic acid yield is poor slightly than the catalyst property that three sections roastings make.
Table 1
| The hydrated alumina trade mark | ????CI | ????SB | ????HB | ????SD-97 | |
| ?Al 2O 3Content, heavy % | ????73 | ????73.3 | ????80.1 | ????73.9 | |
| Pore volume, milliliter/gram | ????0.50 | ????0.92 | ????0.58 | ????0.29 | |
| Specific surface, rice 2/ gram | ????230 | ????352 | ????156 | ????275 | |
| Average pore diameter, nm | ????5.8 | ????10 | ????13.9 | ????4.0 | |
| Pore size distribution, % | ????＜4.4mm | ????5.8 | ????0.4 | ????1.9 | ????53.8 |
| ????4.4～10.6nm | ????89.8 | ????42.82 | ????12.8 | ????35.2 | |
| ????＞10.6nm | ????4.7 | ????56.8 | ????85.2 | ????11.0 | |
Table 2
| Instance number | Bearer number | Specific surface, rice 2/ gram | Pore volume, milliliter/gram | The acid site number, 10 20Individual/gram | Pore size distribution, % | ||
| ???＜6.0nm | ????6.0～12.0nm | ????＞12.0nm | |||||
| 1 | ??a | ????170 | ??0.52 | ????1.0 | ???0.7 | ????87.0 | ????12.3 |
| 2 | ??e | ????195 | ??0.52 | ????1.3 | ???4.0 | ????94.3 | ????1.7 |
| 3 | ??f | ????161 | ??0.51 | ????0.8 | ???0.0 | ????82.9 | ????17.1 |
| Comparative Examples 1 | ??b | ????225 | ??0.42 | ????1.2 | ???5.8 | ????52.7 | ????41.5 |
| Comparative Examples 2 | ??c | ????112 | ??0.63 | ????0.6 | ???2.8 | ????23.4 | ????73.8 |
| Comparative Examples 3 | ??d | ????200 | ??0.34 | ????0.9 | ???45.9 | ????45.6 | ????8.5 |
Table 3
| Instance number | Catalyst number | Bearer number | Platinum content, heavy % | Specific surface, rice 2/ gram | Pore volume, milliliter/gram | Pore size distribution, % | ||
| ???＜6.0nm | ????6.0～12.0nm | ????＞12.0nm | ||||||
| ????4 | ??A | ??a | ????1.2 | ????172 | ??0.51 | ???0.0 | ????87.7 | ????12.3 |
| ????5 | ??E | ??e | ????1.2 | ????198 | ??0.52 | ???4.0 | ????94.0 | ????2.0 |
| ????6 | ??F | ??f | ????1.2 | ????155 | ??0.50 | ???0.9 | ????82.0 | ????17.1 |
| ????7 | ??B | ??b | ????1.2 | ????230 | ??0.43 | ???5.0 | ????53.5 | ????41.5 |
| ????8 | ??C | ??c | ????1.2 | ????120 | ??0.62 | ???2.8 | ????23.5 | ????73.7 |
| ????9 | ??D | ??d | ????1.2 | ????205 | ??0.35 | ???45.2 | ????46.1 | ????8.7 |
| ????10 | ??G | ??a | ????1.2 | ????171 | ??0.51 | ???1.5 | ????87.0 | ????11.5 |
| ????11 | ??H | ??a | ????2.5 | ????168 | ??0.50 | ???3.8 | ????85.2 | ????11.0 |
| ????12 | ??I | ??a | ????0.5 | ????175 | ??0.52 | ???2.3 | ????89.2 | ????13.1 |
Table 4
| Instance number | The catalyst numbering | The benzoic acid conversion ratio, heavy % | Hexahydrobenzene formic acid selectivity, heavy % | Liquid is received, heavy % | Hexahydrobenzene formic acid yield, heavy % |
| ??13 | ????A | ??82.3 | ????95.1 | ????98.2 | ????76.85 |
| ??14 | ????E | ??95.2 | ????76.4 | ????95.4 | ????69.38 |
| ??15 | ????F | ??76.2 | ????98.6 | ????99.0 | ????74.07 |
| ??16 | ????G | ??83.4 | ????85.2 | ????92.3 | ????65.59 |
| ??17 | ????H | ??80.4 | ????94.6 | ????98.5 | ????74.92 |
| ??18 | ????I | ??83.2 | ????95.8 | ????96.4 | ????76.83 |
| ??19 | ????B | ??87.2 | ????84.6 | ????90.5 | ????66.76 |
| ??20 | ????C | ??65.2 | ????93.2 | ????97.6 | ????59.31 |
| ??21 | ????D | ??76.0 | ????86.2 | ????98.5 | ????64.52 |
Claims (10)
1, a kind of benzoic acid hydrogenation prepares the catalyst of hexahydrobenzene formic acid, is made up of the aluminium oxide of supported V IB or VIII family metal, and wherein the content of metal is 0.1～3.0 heavy %, and the specific area of alumina catalyst support is 160～210 meters
2/ gram, pore volume are that 0.5～0.6 milliliter/gram, surface acid center number are 0.2～1.5 * 10
20Individual/gram.
2, according to the described catalyst of claim 1, it is characterized in that described VIII family metal is platinum, palladium, nickel or cobalt, the group vib metal is a molybdenum.
3, according to the described catalyst of claim 1, it is characterized in that the metal in the catalyst is a platinum, its content is 0.5～2.0 heavy %.
4, according to the described catalyst of claim 1, the specific area that it is characterized in that alumina catalyst support is 170～195 meters
2/ gram.
5,, it is characterized in that carrier surface acid site number is 0.7～1.3 * 10 according to the described catalyst of claim 1
20Individual/gram.
6, according to the described catalyst of claim 1, the average pore diameter that it is characterized in that carrier is 7～9 nanometers, and its median pore diameter is that the hole of 6.0～12.0 nanometers is greater than 80%.
7,, it is characterized in that described alumina support is is 230～250 meters by specific area according to the described catalyst of claim 1
2/ gram, the alumina hydrate powder of average pore diameter 5～7 nanometers are through extruded moulding, and dry back makes in 500～1000 ℃ of roastings.
8,, it is characterized in that the sintering temperature behind the described alumina hydrate powder extruded moulding is 600～950 ℃ according to the described catalyst of claim 7.
9,, it is characterized in that this catalyst is that dry back is in 200～550 ℃ of roastings with metal compound solution oxide impregnation alumina supporter according to the described catalyst of claim 1.
10,, it is characterized in that with platinum compounds solution impregnation of alumina carrier, dry back in 200～220 ℃, 350～380 ℃, 500～550 ℃ difference roasting 1～8 hour according to the described catalyst of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011309776A CN1142016C (en) | 2001-08-29 | 2001-08-29 | Catalyst for preparation of hexahydrobenzoic acid by hydrogenation of benzoic acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011309776A CN1142016C (en) | 2001-08-29 | 2001-08-29 | Catalyst for preparation of hexahydrobenzoic acid by hydrogenation of benzoic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1406666A true CN1406666A (en) | 2003-04-02 |
| CN1142016C CN1142016C (en) | 2004-03-17 |
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ID=4670287
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011309776A Expired - Fee Related CN1142016C (en) | 2001-08-29 | 2001-08-29 | Catalyst for preparation of hexahydrobenzoic acid by hydrogenation of benzoic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1142016C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106554281A (en) * | 2015-09-24 | 2017-04-05 | 中国科学院大连化学物理研究所 | A kind of method that methyl benzoate hydrogenation reaction produces cyclohexanecarboxylic acid methyl esters |
| CN114433164A (en) * | 2022-01-26 | 2022-05-06 | 西安凯立新材料股份有限公司 | Method for preparing cyclohexanecarboxylic acid by hydrogenation of benzoic acid under catalysis of fixed bed |
-
2001
- 2001-08-29 CN CNB011309776A patent/CN1142016C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106554281A (en) * | 2015-09-24 | 2017-04-05 | 中国科学院大连化学物理研究所 | A kind of method that methyl benzoate hydrogenation reaction produces cyclohexanecarboxylic acid methyl esters |
| CN114433164A (en) * | 2022-01-26 | 2022-05-06 | 西安凯立新材料股份有限公司 | Method for preparing cyclohexanecarboxylic acid by hydrogenation of benzoic acid under catalysis of fixed bed |
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| Publication number | Publication date |
|---|---|
| CN1142016C (en) | 2004-03-17 |
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Granted publication date: 20040317 Termination date: 20110829 |