CN102451691A - Preparation method of nickel-based hydrogenation catalyst - Google Patents
Preparation method of nickel-based hydrogenation catalyst Download PDFInfo
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- CN102451691A CN102451691A CN2010105142636A CN201010514263A CN102451691A CN 102451691 A CN102451691 A CN 102451691A CN 2010105142636 A CN2010105142636 A CN 2010105142636A CN 201010514263 A CN201010514263 A CN 201010514263A CN 102451691 A CN102451691 A CN 102451691A
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Abstract
The invention discloses a preparation method of a nickel-based hydrogenation catalyst. The preparation method comprises the following steps that carrier alumina and /or silicon oxide, an active metal ingredient and an auxiliary agent ingredient are prepared into slurry; the slurry and a precipitator are added into a reactor in a parallel flow way and are prepared into a catalyst precursor; and the catalyst precursor, a peptizing agent and water are mixed, kneaded, molded, dried and calcined to form the nickel-based hydrogenation catalyst. Through the preparation method, the active metal ingredient can uniformly precipitate on the carrier so that high-uniformity uniformity of the active metal ingredient on the carrier is guaranteed. Through the parallel flow way for precipitation, a uniform precipitation environment in precipitation is obtained so precipitates having the same shape and size are obtained. The nickel-based hydrogenation catalyst obtained by the preparation method can be utilized for hydrogenation decoloration of C5 petroleum resin, C9 petroleum resin and C5-C9 mixed petroleum resin.
Description
Technical field
The present invention relates to a kind of preparation method of nickel-base hydrogenation catalyst, particularly be used for C
5Petropols, C
9Petropols and C
5, C
9Blend hydrogenation of petroleum resin decolouring catalyst.
Background technology
Petropols are the lower functional resins of a kind of relative molecular mass, the characteristic that has tackifying, caking property and mix with other resin.Be widely used in fields such as coating, adhesive, printing-ink, rubber chemicals, paper additive.Petropols can be divided into C according to the difference of raw materials for production and character
5Petropols, C
9Petropols, C
5-C
9Copolymerization tree oil etc.At present; The main source of preparation Petropols is accessory substances of petroleum cracking ethene, and this byproduct is different because of its cracking stock and cracking severity, and output is generally 10%～20% of ethylene product; Because it is backward relatively that cracking stock is formed production technology and production technology complicated and the production Petropols; Cause the color and luster of Petropols dark, poor stability, the existence of especially two keys and phenyl ring influenced the colourity of resin, stability and with the compatibility of other resins, limited its range of application.It is one of petroleum resin modified important means that Petropols are carried out hydrogenation; Be that Petropols are under the condition of hydrogen and catalyst; Make in the Petropols molecule two keys and the part benzene ring hydrogenation saturated, removed Petropols residual halogen element in polymerization process again, improve the color and luster and the photo and thermal stability of Petropols; Improve product quality, expanded the range of application of Petropols.
The hydrogenation of petroleum resin catalyst adopts noble metals such as palladium, platinum as the catalyst activity component usually, and it can limit the adding hydrogen into resin cracking side-reaction effectively.US 4,384,080 and US 4,952,639 the hydrogenation of petroleum resin method of making hydrogenation catalyst with noble metals such as palladium, platinum, rhenium, rutheniums has been described, generally adopting the one pack system metal is the catalyst activity component.US 4,540, and 480 have introduced a kind of hydrogenation of petroleum resin method, and the active component of hydrogenation catalyst used therein adopts noble metal, and the carrier of catalyst is Al
2O
3, it is said that this catalyst has higher active and long service life; CN 02137114.8 discloses a kind of hydrogenation catalyst that is used for by dicyclopentadiene petroleum resin hydrogenation preparing dicyclopentadiene hydrogenated petroleum resin; This catalyst activity component is Pd and Pt; The content of Pd is 0.1wt%～1.0wt%; The content of Pt is 0.05wt%～0.50wt%, and catalyst carrier is γ-Al
2O
3, its specific area is 150～250m
2/ g, pore volume are 0.5～0.9mL/g, and this catalyst reaches very desirable effect aspect the form and aspect of dicyclopentadiene petroleum resin improving.Though noble metal catalyst has stronger alkene, aromatic hydrocarbons saturability; Reaching ideal effect aspect the hydrogenation of petroleum resin decolouring; But there is following shortcoming in noble metal catalyst: at first, noble metal catalyst is higher than the non-precious metal catalyst far away on preparation cost; Secondly, noble metal catalyst is in use to the requirement of impurity content in the raw material, and is particularly harsh especially to the content requirement of sulphur in the raw material.Therefore, the hydrogenation process that adopts noble metal catalyst to carry out must be controlled impurities in raw materials content.
Nickel-base hydrogenation catalyst is cheap; Active higher, have stronger alkene, aromatic hydrocarbons saturability, simultaneously; Can make the organic compound hydrogenolysis of assorted elements such as containing S, N, O in the oil effectively, have wide, the advantages such as liquid yield is high, good product quality of the raw material range of processing.At present, be that the nickel catalyst of carrier also generally is used with diatomite, wherein nickel content is generally 40%～60%, and this catalyst can make the adding hydrogen into resin degraded, and suitable hydrogenation degraded can make the resin intersolubility improve.
The preparation method that nickel-base hydrogenation catalyst is general has: coprecipitation, mechanical mixing, infusion process etc.Coprecipitation is a kind of method that two or more component is precipitated simultaneously.Be characterized in once can obtaining several kinds of components simultaneously, and the distribution of each component is more even.During the immersion process for preparing high-nickel catalyst,, in the catalyst soakage process, need carry out dipping, drying more than twice or twice to carrier for satisfying catalyst content, even roasting, make catalyst strength sharply descend.Adopt mechanical mixing to prepare the catalyst of the pore volume of catalyst less than the coprecipitation preparation; This is owing in catalyst preparation process, add a large amount of active metal salts; Need add a large amount of peptization acid during preparation and carry out peptization and just can make the smooth moulding of catalyst, very big to the pore structure influence of catalyst; And adopt coprecipitation to prepare the catalyst of high tenor, and can overcome these problems effectively, preparation flow is simple, more helps improving the dispersion and the utilization rate of reactive metal.
CN200610064904.6 discloses suitable cracking C
9A kind of nickel series hydrogenating catalyst of cut fraction hydrogenation and preparation method thereof; CN200810113134.9 discloses a kind of non-noble metal hydrogenation catalyst of suitable hydrogenation of petroleum resin and preparation method thereof; These two kinds of catalyst all adopt the coprecipitation method preparation; Wherein the mixed solution with nickel salt and builder salts is heated under the uniform temperature, adds alkaline precipitating agent again, and sediment is processed catalyst through washing, drying, moulding and roasting.This Preparation of catalysts shortcoming is that the deposition environment of precipitation process moment is all inequality, and the grain size that causes being precipitated differs, and influences the activity level performance of nickel, reduces activity of such catalysts; Particularly CN200610064904.6 is in catalyst preparation process, and alumina catalyst support and reactive metal precipitate simultaneously, and reactive metal gets into the lattice of aluminium oxide, causes reactive metal normally not bring into play, and has reduced active utilization rate.
CN200610016260.3 discloses a kind of preparation method who is used for the high-nickel catalyst of the two keys of unsaturated vegetable and animals oils hydrogenation and removing; It is characterized in that the alkaline sedimentation agent solution is put into agitated reactor is heated to 60～70 ℃; Stirring adding soluble nickel salting liquid precipitates; Nickel salt solution adds the back and adds alumina support, stirs washing after 0.5～1.0 hour, drying, pulverizing and roasting high-nickel catalyst.This Preparation of catalysts shortcoming is: at first; In the precipitation process, add in the precipitant solution of acid nickel salt solution alcaliotropism, cause the deposition environment of the precipitation process moment in the agitated reactor all inequality; Be that the pH value of precipitation reaction in agitated reactor is to carry out in the descending earthquake; Thereby the grain size that causes being precipitated differs, and influences the performance of the activity level of nickel, reduces activity of such catalysts; Secondly, deposition finishes the back and adds alumina support, and this process belongs to two kinds of solid matters and mixes, and is unfavorable for the dispersion of nickel sediment at carrier surface, has reduced the utilization rate of reactive metal.
US 4042532 discloses a kind of thermally-stabilised good Ni-Al Preparation of catalysts method; This method is that nickel is mixed with the nickel ammonium salt aqueous solution; Saturated again dipping aluminium hydroxide; At high temperature decompose the ammonium compound then nickel is deposited in the duct and space of aluminium hydroxide, make the skewness of nickel in aluminium oxide.The shortcoming of this method is that precipitation temperature is higher, and the ammonia that discharges in the precipitation process has also caused environmental pollution.
Summary of the invention
In order to overcome weak point of the prior art, the invention provides a kind of preparation method of nickel-base hydrogenation catalyst.This method non-environmental-pollution, active metal nickel is evenly distributed on the catalyst carrier surface in the gained catalyst, has improved the utilization rate of reactive metal, and then has improved activity of such catalysts.
The preparation method of nickel-base hydrogenation catalyst of the present invention comprises:
(1) the predecessor soluble-salt of active component nickel and the predecessor soluble-salt of auxiliary agent are dissolved in the water; Be made into nickeliferous and mixed aqueous solution auxiliary agent, again will be as the aluminium oxide of carrier or/and silica adds nickeliferous and with the mixed aqueous solution of auxiliary agent in form slurries;
(2) will be as the alkali soluble property salt wiring solution-forming of precipitating reagent;
(3) in agitated reactor, add water purification; Startup is stirred and agitated reactor is heated; When temperature of reaction kettle reaches reaction temperature, and stream adds the precipitant solution that slurries that step (1) obtains and step (2) obtain, and the pH value of the interior slurries of control agitated reactor is 6.0～10.0;
(4) after reaction finishes, pH value to 10.0～12.0 of slurries in the adjustment agitated reactor, and under this pH value and temperature conditions, leave standstill;
(5) material of step (4) gained obtains the nickel-base hydrogenation catalyst precursor through filtration, washing, drying;
(6) in the material of step (5), add peptizing agent and mix with water purification and pinch, material mix pinch even after, through extruded moulding, material promptly gets nickel-base hydrogenation catalyst of the present invention through drying, roasting after the moulding.
The nickel-base hydrogenation catalyst of the inventive method gained; Weight with nickel-base hydrogenation catalyst is benchmark; The content of active metal nickel is 20%～70%; Auxiliary agent is 1%～10.0% in the content of oxide, is preferably 3.0%～10.0%, and the content of said alumina catalyst support and/or silica is 20.0%～70.0%.
In the step (1), the concentration of the mixed aqueous solution of said nickeliferous and auxiliary agent is 0.2～1.0mol/L.The predecessor soluble-salt of said active component nickel is one or more in nickel nitrate, nickelous sulfate, nickel chloride and the nickel acetate.The predecessor soluble-salt of said auxiliary agent by the nitrate or and/or the sulfate of adding auxiliary agent.Said alumina catalyst support is or/and silica can be one or more in the aluminium oxide, silica, diatomite, kaolin of boehmite, various crystal formations.
Said auxiliary agent is one or more in IIA family alkaline-earth metal, I B group 4 transition metal, IIB group 4 transition metal, group VIII transition metal and the lanthanide series metal.Among the present invention, described auxiliary agent can be selected according to processing raw material, and preferably can suppress nickel crystallite and increase, and improves catalyst nickel reduction degree and increases the material of catalyst sulfur resistance, like among Fe, Mg, Cu, Zn, Co, La, the Ce one or more.
In the step (2), said alkali soluble property salt is one or more in NaOH, potassium hydroxide, sodium carbonate, potash, sodium acid carbonate and the saleratus, and its concentration is 0.5mol/L～1.5mol/L.
In the step (3), the said water purification amount that in the precipitation reaction still, adds is 10%～30% of step (a 3) gained material cumulative volume; Described reaction temperature is 60 ℃～100 ℃; The said speed that in agitated reactor, adds material is following: the adding speed of step (1) gained slurries is 20mL/min～80mL/min, and the adding speed of step (2) gained alkaline sedimentation agent solution is 40mL/min～100mL/min.
PH value with agitated reactor after the described reaction of step (4) finishes is adjusted to 10.0～12.0, and temperature of reaction kettle remains on 60 ℃～100 ℃, and time of repose is 20 minutes～100 minutes;
In the step (5), described washing is with the water purification washing, and washing finishes when cleaning solution pH is 6.5～7.5.Described drying condition is following: dry 1h～12h in 100～140 ℃ of drying boxes.
In the step (6), described peptizing agent can be one or more in nitric acid, acetic acid and the citric acid.Described catalyst can be column type, trifolium-shaped or bunge bedstraw herb type; Described drying condition is following: dry 1h～12h in 100 ℃～140 ℃ drying boxes; Said roasting condition is: at 300 ℃～650 ℃ following roasting 3h～12h.
The nickel-base hydrogenation catalyst of the inventive method gained can be used for C
5Petropols, C
9Petropols and C
5, C
9In the blend hydrogenation of petroleum resin decolorization, can also be used for co hydrogenation (methanation), steam reformation, vaporization waits the hydrogenation saturation history of reaction and unsaturated hydrocarbons.
The advantage of the inventive method is: slurries that carrier material and active component are processed and alkaline precipitating agent and stream add agitated reactor, have guaranteed active component homogeneous precipitation on carrier, have guaranteed that the height of active component on carrier evenly disperses; Simultaneously,, also guaranteed deposition environment homogeneous in the precipitation process, made sediment exist with identical shaped and grain size owing to adopt and streamed the deposition.The high-nickel catalyst for preparing has two preferably keys and part benzene ring hydrogenation saturability reaches decolorizing effect preferably, is specially adapted to C
5Petropols, C
9Petropols and C
5, C
9Blend hydrogenation of petroleum resin decolouring catalyst.
Description of drawings
Fig. 1 is the XRD figure of embodiment and comparative example gained nickel-base hydrogenation catalyst.
The specific embodiment
Embodiment 1
279.5g six water nickel chlorides, 11.0g lanthanum nitrate hexahydrate are mixed with mixed solution, and making two kinds of salt is 0.6mol/L in the concentration of this solution, after two kinds of salt all dissolve, adds boehmite and (contains Al
2O
370% (mass fraction)) 92.9g, it is for use to process slurries; 318g sodium carbonate is soluble in water, be mixed with the precipitant solution that concentration is 1.0mol/L, for use; In the 8000mL agitated reactor, add the 1000mL water purification in advance, heating is also opened mixing plant, when temperature rises to 80 ℃; Keep temperature in the kettle, beginning and stream add mixed serum and alkaline sedimentation agent solution, and the flow of control mixed serum is 40mL/min and alkaline precipitating agent liquid inventory 55mL/min; Keeping the pH value of slurries in the agitated reactor is 7.2, after the acidic mixed slurries all add, with the alkaline sedimentation agent solution slurry pH value in the agitated reactor is transferred to 10.5; Keep temperature and the pH value of this moment to begin to leave standstill, leave standstill 30 minutes after, filtration removal mother liquor; And wash to remove residual small amounts of water soluble impurity on the sediment with water purification; When washings pH value was 6.5, washing finished, and filter cake placed 120 ℃ of drying boxes dry 3 hours.Take by weighing dry back material 100g; Adding 3.0g nitric acid and 80g water purification mix to be pinched, and mixes the material of pinching and on banded extruder, carries out extruded moulding, and molding materials placed 100 ℃ of drying boxes dry 10 hours; Roasting is 10 hours under 300 ℃ of conditions, promptly gets nickel-base hydrogenation catalyst C
1, its analysis result is seen table 1 and Fig. 1.
Embodiment 2
The preparation process just is changed to 0.3mol/L with two kinds of salt concentration in solution with embodiment 1, and precipitant solution concentration is changed to 1.5mol/L, and the nickel-base hydrogenation catalyst of preparation is C
2, its analysis result is seen table 1.
Embodiment 3
The preparation process is with embodiment 1, with adding the 1500mL water purification in the 8000mL agitated reactor in advance, the nickel-base hydrogenation catalyst C of preparation
3, its analysis result is seen table 1.
Embodiment 4
The preparation process rises to 100 ℃ with embodiment 1 with reactor temperature, after the acidic mixed slurries all add, with the alkaline sedimentation agent solution slurry pH value in the agitated reactor is transferred to 12; Time of repose is extended to 100 minutes, filter and remove mother liquor, and wash to remove residual small amounts of water soluble impurity on the sediment with water purification, washings pH value is 7.0, prepares nickel-base hydrogenation catalyst C
4, its analysis result is seen table 1 and Fig. 1.
Embodiment 5
The preparation process changes also flow the flow that adds mixed serum as 80mL/min and alkaline precipitating agent liquid inventory 100mL/min with embodiment 1 into, and simultaneously the pH value of slurries in the agitated reactor being carried is 9.5, prepares nickel-base hydrogenation catalyst C
5, its analysis result is seen table 1.
Embodiment 6
The preparation process changes boehmite into 65g γ-Al with embodiment 1
2O
3(greater than 150 order powder) are processed slurries; Prepare nickel-base hydrogenation catalyst C
6, its analysis result is seen table 1.
Embodiment 7
The preparation process is with embodiment 1; Mixed solution is processed by 290.8g six water nickel nitrates and 59.4g zinc nitrate and 29.1g copper nitrate; Mixed solution concentration 1.0mol/L; Boehmite is changed to 65g silicon-dioxide powdery (greater than 150 order powder), and the precipitating reagent sodium carbonate liquor changes the sodium hydroxide solution of 1.0mol/L concentration into, makes nickel-base hydrogenation catalyst C
7, analysis result is seen table 1 and Fig. 1.
Embodiment 8
The preparation process is with embodiment 1; Mixed solution is processed by 290.8g six water nickel nitrates and 59.4g zinc nitrate and 29.1g copper nitrate; Mixed solution concentration 1.0mol/L; Boehmite is changed to 50g diatomite powder (greater than 150 order powder), and the precipitating reagent sodium carbonate liquor changes the sodium carbonate and the potash mixed solution of 1.0mol/L concentration into, makes nickel-base hydrogenation catalyst C
8, analysis result is seen table 1.
Embodiment 9
The preparation process (contains Al with embodiment 1 with boehmite
2O
370% (mass fraction)) addition is carried to 363.5g, prepares nickel-base hydrogenation catalyst C
9, its analysis result is seen table 1 and Fig. 1.
Embodiment 10
The preparation process (contains Al with embodiment 1 with boehmite
2O
370% (mass fraction)) addition is reduced to 11.3g, prepares nickel-base hydrogenation catalyst C
10, its analysis result is seen table 1 and Fig. 1.
Embodiment 11
The preparation process changes the peptizing agent in the forming process into 6g acetic acid and 10g citric acid mixed solution with embodiment 1, prepares nickel-base hydrogenation catalyst C
11Its analysis result is seen table 1.
Embodiment 12
The preparation process is descended dry 5 hours with molding materials for 140 ℃ in temperature, and 650 ℃ of following roastings 4 hours, is prepared nickel-base hydrogenation catalyst C with embodiment 1
12Its analysis result sees Table 1 and Fig. 1.
Comparative example
Prepare nickel-base hydrogenation catalyst by CN200610016260.3.
318g sodium carbonate is soluble in water, and the precipitant solution that is mixed with concentration and is 1.0mol/L is put into agitated reactor, when being heated to 70 ℃, keeps temperature in the kettle.279.5g six water nickel chlorides are mixed with the solution that concentration is 0.6mol/L, join in the sodium carbonate liquor in the still and precipitate, precipitate fully up to solution containing nickel.Deposition finishes to add solid alumina 65g, stirs washing after 0.5-1.0 hour, and filter cake placed 120 ℃ of drying boxes dry 3 hours.Take by weighing dry back material 100g; Adding 3.0g nitric acid and 80g water purification mix to be pinched; Mix the material of pinching and on banded extruder, carry out extruded moulding, molding materials placed 120 ℃ of drying boxes dry 3 hours, and roasting is 10 hours under 300 ℃ of conditions; Promptly get nickel-base hydrogenation catalyst B, its analysis result is seen table 1 and Fig. 1.
The physico-chemical property of the nickel-base hydrogenation catalyst of table 1 embodiment and comparative example gained
| Catalyst | C 1 | C 2 | C 3 | C 4 | C 5 | C 6 | C 7 | C 8 | C 9 | C 10 | C 11 | C 12 | B |
| Ni，％ | 37.5 | 36.8 | 38.2 | 37.9 | 38.1 | 44.1 | 34.2 | 37.8 | 20.1 | 69.3 | 38.2 | 37.2 | 32.1 |
| Al 2O 3，％ | 50.2 | 50.3 | 51.9 | 50.8 | 50.9 | 41.3 | 19.8 | 73.4 | 7.9 | 49.3 | 50.8 | 58.1 | |
| SiO 2，％ | - | - | - | - | - | - | 40.5 | 31.3 | - | - | - | - | - |
| La 2O 3，％ | 2.20 | 2.19 | 2.28 | 2.25 | 2.21 | 2.61 | 1.2 | 4.1 | 2.18 | 2.24 | - | ||
| ZnO，％ | - | - | - | - | - | - | 10.1 | 11.0 | - | - | - | - | - |
| CuO，％ | - | - | - | - | - | - | 6.1 | 6.6 | - | - | - | - | |
| Pore volume, mL/g | 0.413 | 0.425 | 0.401 | 0.418 | 0.409 | 0.415 | 0.438 | 0.404 | 0.442 | 0.386 | 0.420 | 0.421 | 0.368 |
| Specific surface, m 2/g | 187 | 194 | 168 | 186 | 176 | 188 | 175 | 205 | 209 | 226 | 192 | 169 | 167 |
Annotate: the percentage in the table 1 is mass fraction
Choose the catalyst C of preparation
1, C
4, C
8, C
12Reach B and on miniature fixed bed hydrogenation reaction unit, estimate, this device has two tandem reactors, and each reactor catalyst loading amount is 10mL; Catalyst was used hydrogen reducing before hydrogenation reaction, reducing condition is following: 380 ℃ of temperature; Hydrogen dividing potential drop 6MPa, the hydrogen volume air speed is 600h
-1, the recovery time is 6 hours.With cyclohexane dissolving C
9Petropols are raw material, and the ratio that Petropols account in the raw material is 10%～50% (mass fraction), and product obtains hydrogenated petroleum resin behind the hydrogenation after cyclohexane is removed in distillation.Petropols character and appreciation condition see Table 2 and table 3, and the product index of each embodiment sees Table 4.
Table 2 Petropols feedstock property
| Resin softening point/℃ | 118 |
| Color (Sai Shi) | 4 # |
| ?S/μg·g -1 | 130 |
| Bromine valency/gBr100mL -1 | 24.14 |
Table 3 evaluating catalyst process conditions
| Reaction pressure/MPa | 8.0 |
| Volume space velocity (with respect to Petropols)/h -1 | 0.6 |
| Hydrogen to oil volume ratio (with respect to Petropols) | 1000 |
| Reaction temperature/℃ | 265 |
The evaluation result of table 4 catalyst
| Catalyst | C 1 | C 4 | C 8 | C 12 | B |
| The hydrogenation resin softening point/℃ | 112 | 112 | 111 | 113 | 109 |
| Form and aspect | Water white | Water white | Water white | Water white | Water white |
| S/μg·g -1 | 0.53 | 0.58 | 0.42 | 0.55 | 0.55 |
| Bromine valency/gBr100mL -1 | 0.966 | 0.869 | 0.724 | 1.09 | 1.69 |
| Double bond conversion rate/% (mass fraction) | 96.0 | 96.4 | 97.0 | 95.5 | 93.0 |
Annotate:
Claims (16)
1. the preparation method of a nickel-base hydrogenation catalyst comprises:
(1) the predecessor soluble-salt of active component nickel and the predecessor soluble-salt of auxiliary agent are dissolved in the water; Be made into nickeliferous and mixed aqueous solution auxiliary agent, again will be as the aluminium oxide of carrier or/and silica adds nickeliferous and with the mixed aqueous solution of auxiliary agent in form slurries;
(2) will be as the alkali soluble property salt wiring solution-forming of precipitating reagent;
(3) in agitated reactor, add water purification; Startup is stirred and agitated reactor is heated; When temperature of reaction kettle reaches reaction temperature, and stream adds the precipitant solution that slurries that step (1) obtains and step (2) obtain, and the pH value of the interior slurries of control agitated reactor is 6.0～10.0;
(4) after reaction finishes, pH value to 10.0～12.0 of slurries in the adjustment agitated reactor, and under this pH value and temperature conditions, leave standstill;
(5) material of step (4) gained obtains the nickel-base hydrogenation catalyst precursor through filtration, washing, drying;
(6) in the material of step (5), add peptizing agent and mix with water purification and pinch, material mix pinch even after, through extruded moulding, material obtains nickel-base hydrogenation catalyst through drying, roasting after the moulding.
2. according to the described method of claim 1; Weight with nickel-base hydrogenation catalyst is benchmark; The content of active metal nickel is 20%～70%, and auxiliary agent is 1%～10.0% in the content of oxide, and the content of said alumina catalyst support and/or silica is 20.0%～70.0%.
3. according to claim 1 or 2 described methods, it is characterized in that said auxiliary agent is one or more in II family alkaline-earth metal, I B group 4 transition metal, IIB group 4 transition metal, group VIII transition metal and the lanthanide series metal.
4. according to claim 1 or 2 described methods, it is characterized in that said auxiliary agent is one or more among Fe, Mg, Cu, Zn, Co, La, the Ce.
5. according to the described method of claim 2, it is characterized in that said auxiliary agent is 3.0%～10.0% in the weight content of oxide in nickel-base hydrogenation catalyst.
6. according to the described method of claim 1, the predecessor soluble-salt that it is characterized in that said active component nickel is one or more in nickel nitrate, nickelous sulfate, nickel chloride and the nickel acetate; The predecessor soluble-salt of said auxiliary agent by the nitrate or and/or the sulfate of adding auxiliary agent.
7. according to the described method of claim 1, it is characterized in that the concentration of the mixed aqueous solution of said nickeliferous and auxiliary agent is 0.2～1.0mol/L.
8. according to the described method of claim 1, it is characterized in that said alumina catalyst support or/and silica is one or more in the aluminium oxide, silica, diatomite, kaolin of boehmite, various crystal formations.
9. according to the described method of claim 1; It is characterized in that in the step (2); Said alkali soluble property salt is one or more in NaOH, potassium hydroxide, sodium carbonate, potash, sodium acid carbonate and the saleratus, and its concentration is 0.5mol/L～1.5mol/L.
10. according to the described method of claim 1, it is characterized in that in the step (3) that the said water purification amount that in the precipitation reaction still, adds is 10%～30% of step (a 3) gained material cumulative volume.
11., it is characterized in that in the step (3) that described reaction temperature is 60 ℃～100 ℃ according to the described method of claim 1.
12. according to the described method of claim 1; It is characterized in that in the step (3); The said speed that in agitated reactor, adds material is: the adding speed of step (1) gained slurries is 20mL/min～80mL/min, and the adding speed of step (2) gained alkaline sedimentation agent solution is 40mL/min～100mL/min.
13. according to the described method of claim 1, it is characterized in that being 10.0～12.0 in the pH value in the step (4), under 60 ℃～100 ℃ conditions of temperature of reaction kettle, time of repose is 20 minutes～100 minutes.
14., it is characterized in that in the step (5) that said washing is with the water purification washing according to the described method of claim 1, washing finishes when cleaning solution pH is 6.5～7.5.
15., it is characterized in that described drying condition is following in the step (5): at 100～140 ℃ of dry 1h～12h according to the described method of claim 1.
16. according to the described method of claim 1, it is characterized in that described drying condition is following in the step (6): at 100 ℃～140 ℃ dry 1h～12h; Said roasting condition is: at 300 ℃～650 ℃ following roasting 3h～12h.
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| CN103386308A (en) * | 2013-07-27 | 2013-11-13 | 西安凯立化工有限公司 | Nickel catalyst for C5 petroleum resin hydrogenation as well as preparation method and application thereof |
| CN104117359A (en) * | 2013-04-27 | 2014-10-29 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN104549287A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Nickel-based catalyst and preparation method thereof |
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