CN1047375C - Saturation hydrogenation method for olefines or aromatic hydrocarbon - Google Patents
Saturation hydrogenation method for olefines or aromatic hydrocarbon Download PDFInfo
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- CN1047375C CN1047375C CN95116430A CN95116430A CN1047375C CN 1047375 C CN1047375 C CN 1047375C CN 95116430 A CN95116430 A CN 95116430A CN 95116430 A CN95116430 A CN 95116430A CN 1047375 C CN1047375 C CN 1047375C
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
Abstract
The present invention relates to a saturation hydrogenation method for olefines or aromatics. Under the technological conditions of a saturation hydrogenation reaction, olefines or aromatics are in contact with a Ni-RE-P amorphous alloy catalyst with a large surface. The specific surface area of the catalyst is 50 to 130 sq. m/g, and the catalyst is composed of 86 to 92.5 wt% of nickel, 0 to 3 wt% of rare earth and phosphorus as the rest. Compared with the hydrogenation method with raney nickel as a catalyst, the hydrogenation method provided by the present invention has higher conversion rate of olefines or aromatics, and lower reaction temperature or lesser catalyst consumption.
Description
The present invention relates to the saturation hydrogenation method of a kind of alkene or aromatic hydrocarbons, more particularly, the present invention relates to the big surperficial Ni-RE-P amorphous alloy of a kind of usefulness as the alkene of catalyzer or the saturation hydrogenation method of aromatic hydrocarbons.
The saturated hydrogenation of alkene or aromatic hydrocarbons is an important commercial run, in petrochemical complex, fine chemistry industry, fields such as pharmacy have a wide range of applications, in numerous hydrogenation catalysts, amorphous alloy is the novel catalytic material of a class, main hydrogenation catalyst as carbon monoxide and unsaturated hydrocarbons, at carbon monoxide (Adv.catal.36,344-357,1989), alkene (chemical journal 47,237,1989), all shown the catalytic activity higher in the hydrogenation reaction of alkynes (J.catal.101,67,1986) than corresponding crystal alloy, yet, because specific surface is little, its catalytic activity is lower than Raney nickel (Raney Ni) hydrogenation catalyst in industrial widespread use, and this has just limited it in industrial application.
In order to overcome the little shortcoming of amorphous alloy specific surface, the method of various its specific surfaces of raising is arisen at the historic moment, as preparing the method (JP86119606) of powdery Ni-P amorphous alloy, the method for mechanical powder process in the presence of at reductive agent, method (EP 173088) with hydrofluoric acid treatment, method (J.Chem.Soc., FaradayTrans.I, 81 that redox is handled, 2485-2493,1985) etc., still, with the specific surface of the amorphous alloy of above-mentioned prepared in various methods also all not above 10 meters
2/ gram.For this reason, CN1073726A adopt with aluminium in advance with the Ni/Fe/Co-RE-P alloying, remove wherein the method for aluminium with sodium hydroxide again through fast quenching and prepare a kind of big surface amorphous alloy, its specific surface can reach 50～130 meters
2/ gram, the practical application of this big surface amorphous alloy that huge surface-area like this makes becomes possibility.
The purpose of this invention is to provide and a kind ofly use big surface amorphous alloy as the alkene of catalyzer or the saturation hydrogenation method of aromatic hydrocarbons.
The said big surface amorphous alloy catalyst of the present invention is meant the Ni-RE-P amorphous alloy catalyst, it consists of the nickel of 86～92.5 heavy %, the rare earth (RE) of 0～3 heavy % and the phosphorus of surplus, wherein, RE is selected from La, Ce, Y, Sm or its mixture, and its specific surface is 50～130 meters
2/ gram.
The said big surperficial Ni-RE-P amorphous alloy catalyst of the present invention can follow these steps to preparation:
1. preparation Ni-P mother alloy will add in the quantitative phosphorus after the quantitative nickel fusion, and the two is alloying voluntarily.
2. in above-mentioned mother alloy, add the rare earth element that is selected from La, Ce, Y, Sm or its mixture of 0～3 heavy %, and in vacuum smelting furnace, refine, obtain the equally distributed Ni-RE-P mother alloy of rare earth element.
3. the aluminium that weight such as adds in the Ni-RE-P mother alloy, vacuum are refined into the mother alloy that Ni-RE-P and aluminium respectively account for 50 heavy %, are designated as (Ni-RE-P)
50Al
50
4. with vacuum quench fast quenching (Ni-RE-P)
50Al
50Mother alloy, fast quenching condition are copper roller linear velocity 20～40 meter per seconds, spraying pressure 0.05～0.1MPa, 1000～1400 ℃ of injection temperatures.
5. with fast quenching gained (Ni-RE-P)
50Al
50Place 10～25 heavy % sodium hydroxide solutions, placed 0-2 hour at 0～50 ℃, be warming up to 50～110 ℃ of constant temperature and handled 1-5 hour, be prepared into big surperficial Ni-RE-P amorphous alloy catalyst, wherein the consumption of sodium hydroxide is advisable with every moles, of aluminum per mole of titanium metal consumption 1.1～1.3 molar sodium hydroxides.
The saturation hydrogenation method of alkene provided by the invention or aromatic hydrocarbons.Can in batch reactor, carry out, also can in fixed bed or other existing reactors, carry out.
Said alkene is meant monoene, diene, polyenoid in the saturation hydrogenation method of alkene provided by the invention or aromatic hydrocarbons; Chain alkene, cyclic olefin or their mixture.Said aromatic hydrocarbons is meant and contains the aromatic hydrocarbon based of benzene, naphthalene, anthracene, indenes, luxuriant and rich with fragrance structure or their mixture.
The processing condition of the saturation hydrogenation method of alkene provided by the invention are temperature of reaction 25 (room temperature)～250 ℃, reaction pressure 1-4MPa, agent material weight ratio (the weight amount of catalyzer and reaction mass than) 0.001～0.2.
The processing condition of aromatic saturated hydrogenation method provided by the invention are 80～250 ℃ of temperature of reaction, reaction pressure 1-4MPa, agent material weight ratio 0.001～0.2.
In the saturation hydrogenation method of alkene provided by the invention or aromatic hydrocarbons, owing to having adopted big surperficial Ni-RE-P amorphous alloy to have alkene or aromatics conversion rate higher when being catalyzer with the Raney nickel as catalyzer, lower temperature of reaction or catalyst levels still less, as in the mixed olefins hydrogenation reaction, adopt the bromine valency of the product that two parts big surface amorphous alloy catalysts and three parts of Raney nickel catalysts obtain identical; And for example, generate in the reaction of methylcyclohexane at 160 ℃ of carapax et plastruw testudinis benzene hydrogenations, the transformation efficiency of toluene is 41.7 heavy % when adopting method of hydrotreating provided by the invention, and toluene conversion has only 17.0 heavy % when adopting Raney nickel as the method for hydrotreating of catalyzer, and the former is 2.5 times of the latter.
The following examples will the invention will be further described.
Among the embodiment, the hydrogenation reaction of alkene and aromatic hydrocarbons is all carried out in 100 milliliters of batch reactors, and reaction pressure is the pressure of hydrogen in the reaction system.Hp-5890 chromatographic instrument and the analysis of HP-5985 chromatograph mass spectrometer are all adopted in the analysis of reactant and reaction product The Nomenclature Composition and Structure of Complexes except that specified otherwise.The specific surface of catalyzer refers to the BET specific surface, measures with ASAP2400 static capacity absorption instrument, and adsorbate is a liquid nitrogen.
Example 1-10
The preparation of big surperficial Ni-RE-P amorphous alloy catalyst.
(1) phosphorus with predetermined amount is placed on compacting in the crucible, pours in the crucible that phosphorus is housed after nickel (technical pure) fusion with predetermined amount, and nickel and phosphorus is alloying voluntarily, gets the Ni-P mother alloy after the cooling.
(2) the Ni-P mother alloy is smashed to pieces, the rare-earth elements La (technical pure, Jinchuan, Gansu non-ferrous metal main office) that adds different amounts respectively, Ce (technical pure, Jinchuan, Gansu non-ferrous metal main office), or mishmetal (Ce 80 heavy %, Le, Y, the heavy % of Sm20, technical pure, Jinchuan, Gansu non-ferrous metal main office), place vacuum toggle stove then, treat to stop 10 minutes after its fusion again, vacuum tightness is 10 in this stove
-1～10
-2Torr, temperature are 1300 ℃, charge into argon gas to normal pressure then and make the Ni-RE-P mother alloy.
(3) with the Ni-RE-P mother alloy with etc. the aluminium (technical pure) of weight mix, set by step the method for (2) refine (Ni-RE-P)
50Al
50Mother alloy.
(4) with vacuum quench (open clear 61-212332 referring to the spy and reach wherein Fig. 2) preparation fast quenching (Ni-RE-P)
50Al
50, the fast quenching condition is copper roller linear velocity 35 meter per seconds, spraying pressure 0.08MPa, 1350 ℃ of injection temperatures.
(5) remove fast quenching (Ni-RE-P)
50Al
50In aluminium, with the fast quenching (Ni-RE-P) that makes
50Al
501 gram is put into and is equipped with 250 milliliters, in the beaker of 20 heavy % sodium hydroxide solutions, at room temperature places 30 minutes, be warming up to 50～105 ℃ then, and constant temperature 1.5 hours, surperficial greatly Ni-RE-P amorphous alloy catalyst, be designated as A, B, C, D, E, F, G, H, I, J.
Table 1 has provided the composition of catalyst A-J, takes out aluminium temperature and specific surface.
Comparative Examples 1-2
The preparation of Raney nickel catalyst.
Get 1 gram Al-Ni alloy (technical pure, Shanghai reagent head factory, contain the heavy % of Ni50) reference literature (" Preparation of Catalyst handbook, Chemical Industry Press, P608～609,1982) method of W-1 and W-4 is prepared into Raney nickel catalyst, is designated as K and L, and that has listed K and L in the table 1 takes out aluminum strip spare and specific surface.
Table 1
| The catalyzer numbering | Catalyzer is formed heavy % | Take out aluminium temperature ℃ | Specific surface m 2/g | |
| Example 1 example 2 examples 3 examples 4 examples 5 examples 6 examples 7 examples 8 examples 9 examples 10 Comparative Examples 1 Comparative Examples 2 | A B C D E F G H I J K L | Ni87.6P12.4 Ni87.6P12.4 Ni87.4La0.4P12.2 Ni87.4RE0.3P12.3 Ni87.4RE0.3P12.3 Ni87.4RE0.3P12.3 Ni87.4RE0.3P12.3 Ni91.9RE0.3P7.8 Ni85.7La2.5P11.8 Ni87.5Ce0.5P12.0 Ni Ni | 105 95 95 95 50 60 70 80 70 70 95 50 | 106 97 76 106 101 103 107 105 103 95 110 105 |
Example 11-14
The vinylbenzene hydrogenation generates the influence of temperature of reaction in the ethylbenzene reaction.
Catalyst system therefor is A and K, and containing the cinnamic cyclohexane solution of 30 volume % with 50 milliliters is reaction solution, 80～110 ℃ of temperature of reaction, and reaction pressure 4.0MPa, stir speed (S.S.) 29 times/minute, in 1 hour reaction times, the results are shown in Table 2.
The presentation of results of table 2, adopt method of hydrotreating provided by the invention, when temperature of reaction was lower than 100 ℃, the styrene conversion rate was suitable as the method for catalyzer with the employing Raney nickel, and temperature of reaction is when being higher than 100 ℃, and the styrene conversion rate is apparently higher than the method that adopts Raney nickel as catalyzer.
Table 2
| Catalyzer | Temperature of reaction ℃ | The heavy % of styrene conversion rate | |
| Example 11 examples 12 examples 13 examples 14 | A | 80 90 100 110 | 56.4 67.0 85.4 100 |
| Comparative Examples 3 Comparative Examples 4 Comparative Examples 5 Comparative Examples 6 | K | 80 90 100 110 | 57.0 67.5 76.7 96.0 |
Example 15-22
The influence of reaction pressure in the mixed olefins hydrogenation reaction.
Catalyst system therefor is D and L, is reactant with 50 milliliters of mixed olefins, mixed olefins consist of C
4Alkene accounts for 13.6 heavy %, and 2,4,4-2,4,4-Trimethyl-1-pentene-1 accounts for 56.0 heavy %, and 2,4,4-2,4,4-Trimethyl-1-pentene-2 accounts for 16.0 heavy %, other C
8Alkene accounts for 9.5 heavy %, C
12Alkene accounts for 4.9 heavy %, the bromine valency of mixed olefins is that 131 (the bromine valency is represented presence of unsaturates, its measuring method is referring to " petrochemical complex analytical procedure " RIPP test method, Science Press, P172-175,1990), the mixed olefins hydrogenation conditions is temperature of reaction 100 and 120 ℃, reaction pressure 23～4.0MPa, stir speed (S.S.) 44 times/minute, in 1 hour reaction times, reaction result is listed in the table 3.
The presentation of results of table 3, adopt method of hydrotreating provided by the invention under different reaction pressures, reactant bromine valency decline scope is all significantly greater than the method for hydrotreating that adopts Raney nickel as catalyzer, it is not obvious to improving olefin conversion to increase reaction pressure, and the reaction pressure of method of hydrotreating provided by the invention can change in a big way.
Table 3
| Catalyzer | Temperature of reaction ℃ | Reaction pressure MPa | Product bromine valency g/100g | |
| Example 15 examples 16 examples 17 examples 18 examples 19 examples 20 examples 21 examples 22 | D | 100 | 2.5 3.0 3.5 4.0 | 75.8 81.7 104 61.8 |
| 120 | 2.5 3.0 3.5 4.0 | 54.2 72.8 94.0 49.3 | ||
| Comparative Examples 7 Comparative Examples 8 Comparative Examples 9 Comparative Examples 10 Comparative Examples 11 Comparative Examples 12 Comparative Examples 13 Comparative Examples 14 | L | 100 | 2.5 3.0 3.5 4.0 | 112 88.9 105 86.9 |
| 120 | 2.5 3.0 3.5 4.0 | 106 84.9 90.4 73.3 |
Example 23-26
The influence of temperature of reaction in the mixed olefins hydrogenation reaction.
Catalyst system therefor be the D reaction conditions with example 17, just temperature of reaction is respectively 100 ℃, 120 ℃, 140 ℃ and 160 ℃, the results are shown in Table 4.
The presentation of results of table 4 adopts method of hydrotreating provided by the invention under different temperature of reaction, and the bromine valency of reactant is all descended significantly, increases temperature of reaction and can improve olefin conversion, and temperature of reaction can change in a big way.
Table 4
| Catalyzer | Temperature of reaction ℃ | Product bromine valency g/100g | |
| Example 23 examples 24 examples 25 examples 26 | D | 100 120 140 160 | 104 94.0 83.8 87.0 |
Example 27-29
The mixed olefins hydrogenation reaction, the influence of catalyzer middle-weight rare earths component.
Catalyst system therefor is G, I, J and L, and reaction conditions is with example 17, and just the reaction times is 3.5 hours, and the results are shown in Table 5.
The presentation of results of table 5, in the big surperficial Ni-RE-P amorphous alloy catalyst that method of hydrotreating provided by the invention adopted, no matter RE is the mixture of La, Ce or La, Ce, Y, Sm, its hydrogenation activity all is better than Raney nickel catalyst greatly.
Table 5
| Catalyzer | Product bromine valency g/100g | |
| Example 27 examples 28 examples 29 Comparative Examples 15 | G I J L | 59.9 51.6 55.0 81.4 |
Example 30
Catalyst levels in the mixed olefins hydrogenation reaction.
Catalyst system therefor is H and L, and the consumption that is Raney nickel catalyst L is 1.5 times of big surface amorphous alloy catalyst H consumption, and reaction conditions is with example 27, and the results are shown in Table 6.
The presentation of results of table 6, in the mixed olefins hydrogenation reaction, olefin conversion and suitable when adopting three parts of Raney nickel catalysts when adopting two parts big surface amorphous alloys as catalyzer, when promptly adopting method of hydrotreating catalyst levels provided by the invention to be reduced to 67 weight % of Raney nickel catalyst consumption, still can reach the effect when adopting Raney nickel to make catalyzer.
Table 6
| Catalyzer | Product bromine valency g/100g | |
| Example 30 Comparative Examples 16 | H L | 59.9 60.1 |
Example 31
The hydrogenation reaction of carbon hexadecylene.
Catalyst system therefor is G and L, and catalyst levels is 2.5 times of catalyst levels of example 7 preparation, and reactant is 50 milliliters of stock liquids that contain 98.5 heavy % carbon hexadecylenes, and it consists of 2,2,4,4,6,8,8-seven methyl nonenes-5 account for 50.2 heavy %, 2,2,4,4,6,8,8-seven methyl nonenes-6 account for 11.8 heavy %, 2,2,4,4,8,8-hexamethyl-6-methyne nonane accounts for 36.5 heavy %, and stock liquid bromine valency is 75.0.Reaction conditions is 230 ℃ of temperature of reaction, reaction pressure 4.0MPa, and stir speed (S.S.) 44 times/minute, in 100 hours reaction times, the results are shown in Table 7.
The presentation of results of table 7 is for C
16The hydrogenation reaction of alkene adopts the saturated hydrogenation effect of method provided by the invention also to be much better than Raney nickel catalyst.
Table 7
| Catalyzer | Product bromine valency g/100g | |
| Example 31 Comparative Examples 17 | G L | ＜0.01 0.04 |
Example 32
The hydrogenation reaction of cyclopentadiene.
Catalyst system therefor is D and L, and reactant is a cyclopentadiene, and reaction conditions is temperature of reaction room temperature (25 ℃), reaction pressure 3.0MPa, and stir speed (S.S.) 44 times/minute, in 1 hour reaction times, the results are shown in Table 8.
The presentation of results of table 8 can carry out under the method for hydrotreating room temperature provided by the invention, and the activity of the big surperficial Ni-RE-P amorphous alloy catalyst that is adopted is higher than Raney nickel catalyst.
Table 8
| Catalyzer | The heavy % of pentamethylene productive rate | The heavy % of cyclopentenes productive rate | |
| Example 32 | D | 95.4 | 2.5 |
| Comparative Examples 18 | L | 90.0 | 1.3 |
Example 33-35
The influence of agent material weight ratio.
Catalyst system therefor is D, and reactant and reaction conditions are with example 17, and just temperature of reaction is 80 ℃, and the results are shown in Table 9.
The presentation of results of table 9, in the method for hydrotreating provided by the invention, the weight ratio of catalyzer and reaction mass can change in a big way, and its scope can from 0.001 to 0.2.
Table 9
| Agent material weight ratio g/g | Product bromine valency g/100g | |
| Example 33 examples 34 examples 35 | 0.005 0.05 0.15 | 87.0 52.4 32.6 |
Example 36-47
The toluene hydrogenation generates the influence of temperature of reaction in the methylcyclohexane reaction.Catalyst system therefor is A, B, C and K, is reaction solution with the cyclohexane solution of 50 milliliter of 30 volume % toluene, and reaction conditions is 120 ℃ of temperature of reaction, 160 ℃, 200 ℃, 240 ℃, reaction pressure 2.0MPa, stir speed (S.S.) 29 times/minute, in 1 hour reaction times, the results are shown in Table 10.
The presentation of results of table 10, the toluene conversion that adopts method of hydrotreating provided by the invention to obtain is significantly higher than with the method for Raney nickel as catalyzer on the one hand, when being 160 ℃ as temperature of reaction, adopt method of hydrotreating provided by the invention, the transformation efficiency that obtains toluene when making catalyzer with C has only 17.0 heavy % when being 41.7 heavy % and the utmost point with Raney nickel as the method for hydrotreating of catalyzer, the former is 2.5 times of the latter; On the other hand, adopt method of hydrotreating provided by the invention can reduce the temperature of reaction, as adopt method of hydrotreating provided by the invention, make catalyzer with C, when temperature of reaction was 160 ℃, the transformation efficiency of toluene was 41.7 heavy %, and adopts Raney nickel as the catalyst hydrogenation method, when temperature of reaction was 240 ℃, the transformation efficiency of toluene had only 28.2 heavy %; Moreover, adopt the increase of temperature of reaction in the method for hydrotreating provided by the invention can improve the transformation efficiency of reactant, temperature of reaction can be in change in a big way.
Table 10
| Catalyzer | Temperature of reaction ℃ | The heavy % of toluene conversion | |
| Example 36 examples 37 examples 38 examples 39 | A | 120 160 200 240 | 7.7 19.1 23.3 25.9 |
| Example 40 examples 41 examples 42 examples 43 | B | 120 160 200 240 | 9.6 36.2 40.2 43.2 |
| Example 44 examples 45 examples 46 examples 47 | C | 120 160 200 240 | 11.9 41.7 45.1 51.6 |
| Comparative Examples 19 Comparative Examples 20 Comparative Examples 21 Comparative Examples 22 | K | 120 160 200 240 | 5.8 17.0 26.1 28.2 |
Example 48
The toluene hydrogenation generates the reaction of methylcyclohexane.
Catalyzer is C and K, and reaction conditions is with example 44, and just temperature of reaction is 140 ℃, the reaction times difference, and the results are shown in Table 11.
The presentation of results of table 11, adopt method of hydrotreating provided by the invention, the hydrogenation reaction of toluene toluene of 100% after 5.5 hours is converted into methylcyclohexane, and adopt Raney nickel as the method for hydrotreating reaction of catalyzer after 7 hours, only make the toluene of 44.6 heavy % be converted into methylcyclohexane, the efficient of method of hydrotreating provided by the invention is far above the method for hydrotreating of using Raney nickel as catalyzer.
Table 11
| Catalyzer | Reaction times hour | The heavy % of toluene conversion | |
| Example 48 Comparative Examples 23 | C K | 5.5 7 | 100 44.6 |
Example 49
The hydrogenation reaction of naphthane.
Catalyzer is G and K, and catalyst levels is 2 times of catalytic amount of example 7 preparation, and reactant is 50 milliliters of tetralines, and reaction conditions is 160 ℃ of temperature of reaction, reaction pressure 4.0MPa, and stir speed (S.S.) 44 times/minute, in 4 hours reaction times, the results are shown in Table 12.
The presentation of results of table 12, for the tetraline hydrogenation reaction, the transformation efficiency of naphthane is significantly higher than with the method for Raney nickel as catalyzer when adopting method of hydrotreating provided by the invention.
Table 12
| Catalyzer | Reaction product is formed heavy % | |||
| Suitable-the naphthane naphthalene | Instead-naphthane | Octahydroization | ||
| Example 49 Comparative Examples 24 | G K | 22.8 13.8 | 11.7 6.4 | 1.3 0.4 |
Example 50
Luxuriant and rich with fragrance hydrogenation reaction.
Catalyst system therefor is H and K, and reactant is that 10 gram phenanthrene are dissolved in the solution that is made in 50 milliliters of toluene, and reaction conditions is 100 ℃ of temperature of reaction, reaction pressure 4.0MPa, and stir speed (S.S.) 44 times/minute, in 3 hours reaction times, the results are shown in Table 13.
The presentation of results of table 13, for the hydrogenation reaction of phenanthrene, the transformation efficiency of phenanthrene is significantly higher than with the method for Raney nickel as catalyzer when adopting method of hydrotreating provided by the invention.
Table 13
| Catalyzer | Reaction product is formed heavy % | |||
| The dihydro phenanthrene | Tetanthrene | Octalin | ||
| Example 50 Comparative Examples 25 | H K | 12.3 5.1 | 8.5 5.1 | 3.0 3.6 |
Claims (6)
1. the saturation hydrogenation method of an alkene, it is characterized in that this alkene contacts with a kind of big surperficial Ni-RE-P amorphous alloy catalyst under the olefine saturation hydrogenation reaction process condition, the nickel that consists of 86～92.5 heavy % of described catalyzer, the rare earth of 0～3 heavy % and the phosphorus of surplus, the specific surface of this catalyzer is 50～130 meters
2/ gram, rare earth wherein is selected from La, Ce, Y, Sm or its mixture.
2. the saturation hydrogenation method of an aromatic hydrocarbons, it is characterized in that this aromatic hydrocarbons contacts with a kind of big surperficial Ni-RE-P amorphous alloy catalyst under the aromatic saturated hydrogenation reaction process condition, the nickel that consists of 86～92.5 heavy % of described catalyzer, the rare earth of 0～3 heavy % and the phosphorus of surplus, the specific surface of this catalyzer is 50～130 meters
2/ gram, rare earth wherein is selected from La, Ce, Y, Sm or its mixture.
3. method of hydrotreating according to claim 1 is characterized in that described alkene is meant monoene, diene, polyenoid; Chain alkene, cyclic olefin or their mixture.
4. method of hydrotreating according to claim 1 is characterized in that described reaction process condition is: 25～250 ℃ of temperature of reaction, reaction pressure 1～4MPa, agent material weight ratio 0.001～0.2.
5. method of hydrotreating according to claim 2, it is characterized in that described aromatic hydrocarbons is meant contains the aromatic hydrocarbon based of benzene, naphthalene, indenes, luxuriant and rich with fragrance structure or their mixture.
6. method of hydrotreating according to claim 2 is characterized in that described reaction process condition is: 80～250 ℃ of temperature of reaction, reaction pressure 1～4MPa, agent material weight ratio 0.001～0.2.
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|---|---|---|---|
| CN95116430A CN1047375C (en) | 1995-09-26 | 1995-09-26 | Saturation hydrogenation method for olefines or aromatic hydrocarbon |
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|---|---|---|---|
| CN95116430A CN1047375C (en) | 1995-09-26 | 1995-09-26 | Saturation hydrogenation method for olefines or aromatic hydrocarbon |
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| CN1047375C true CN1047375C (en) | 1999-12-15 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1072029C (en) * | 1997-06-04 | 2001-10-03 | 中国石油化工总公司 | Catalyst containing Ni-P non-crystalline-state alloy, preparation method and application thereof |
| CN1075401C (en) * | 1997-07-10 | 2001-11-28 | 中国石油化工总公司 | Non-crystalline catalyst containing Ni and P it prepn. method and application |
| CN1078095C (en) * | 1998-05-06 | 2002-01-23 | 中国石油化工集团公司 | Amorphous alloy catalyst containing nickel and phosphorus and preparation method thereof |
| CN1093003C (en) * | 1999-04-29 | 2002-10-23 | 中国石油化工集团公司 | Hydrorefining catalyst and its preparation method |
| KR100416404B1 (en) | 1999-04-29 | 2004-01-31 | 차이나 피트로케미컬 코포레이션 | A hydrogenation catalyst and its preparation |
| CN103030487B (en) * | 2011-09-29 | 2016-02-10 | 中国石油化工股份有限公司 | The method that aromatic hydrogenation is saturated |
| RU2717334C1 (en) * | 2016-11-30 | 2020-03-23 | Чайна Петролиум энд Кемикал Корпорейшн | Method of producing hexadecahydropyrene |
| CN110684554A (en) * | 2019-11-12 | 2020-01-14 | 南京大学连云港高新技术研究院 | Preparation method for improving saturated hydrocarbon content of plastic pyrolysis oil |
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| US4560816A (en) * | 1982-06-01 | 1985-12-24 | University Of South Carolina | Catalyzed hydrogenation and dehydrogenation processes |
| CN1073726A (en) * | 1991-12-24 | 1993-06-30 | 中国石油化工总公司石油化工科学研究院 | Large specific surface amorphous alloy and preparation thereof |
| EP0554765A1 (en) * | 1992-02-05 | 1993-08-11 | BASF Aktiengesellschaft | Process for preparing cyclohexene by partial hydrogenation of benzene |
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- 1995-09-26 CN CN95116430A patent/CN1047375C/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4560816A (en) * | 1982-06-01 | 1985-12-24 | University Of South Carolina | Catalyzed hydrogenation and dehydrogenation processes |
| CN1073726A (en) * | 1991-12-24 | 1993-06-30 | 中国石油化工总公司石油化工科学研究院 | Large specific surface amorphous alloy and preparation thereof |
| EP0554765A1 (en) * | 1992-02-05 | 1993-08-11 | BASF Aktiengesellschaft | Process for preparing cyclohexene by partial hydrogenation of benzene |
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