CN1597098A - Preparing of cyclobexene catalyst for benzene selective hydrogenation its preparation method and regulating method and regeneration method - Google Patents

Preparing of cyclobexene catalyst for benzene selective hydrogenation its preparation method and regulating method and regeneration method Download PDF

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CN1597098A
CN1597098A CNA2004100604510A CN200410060451A CN1597098A CN 1597098 A CN1597098 A CN 1597098A CN A2004100604510 A CNA2004100604510 A CN A2004100604510A CN 200410060451 A CN200410060451 A CN 200410060451A CN 1597098 A CN1597098 A CN 1597098A
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selective hydrogenation
catalyst
hydrogenation catalyst
benzene
benzene selective
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CN1304109C (en
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刘寿长
李利民
王向宇
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Zhengzhou University
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Zhengzhou University
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Abstract

A catalyst able to be modified or regenerated by washing it with the purified water containing H2O2 and treating it by diluted acid can be used for preparing cyclohexane from benzene by selective hydrogenating. It contains an active component Ru, a RE element La or transition element Zn or Fe and a disperser, and is prepared by chemical reduction method or deposition method.

Description

Specification producing cyclohexene with benzene selective hydrogenation catalyst, its preparation method and modulating method and renovation process
Affiliated field:
The invention belongs to and comprise metal, the catalyst of oxide or hydroxide is specifically related to a kind of producing cyclohexene with benzene selective hydrogenation catalyst, its preparation method and modulating method and renovation process.
Technical background:
From 1972 so far, have about the patent of preparing cyclohexene from benzene added with hydrogen 100 multinomial.As Chinese patent CN93103689.5, CN 93103687.9, CN94119103.6 etc.U.S. Pat 3912787, US4575572, US 4678861, US 4734536 etc.Japan Patent JP[95,165,646], JP[96,125,171] and, JP[97,12,484], JP[98,139,692] etc., world patent WO 92/03379, WO 93/16972 etc., European patent EP 0552809A1, EP 0170915A2 etc.
Existing patented technology, the most technology of Preparation of Catalyst are comparatively complicated, for industrialization has brought difficulty.Most patent catalyst activity selectivity are lower simultaneously, still do not possess industrial application value.Many patent emphasis are the corresponding cycloolefin technology of aromatic hydrocarbons partial hydrogenation system.Though the patent that has relates to the catalyst regeneration technology, to different catalyst, renovation process does not often have universality.Seldom there is patent to relate to the adjustable sex change problem of catalyst.As U.S. Pat 3912787 " the selection partial hydrogenation of aromatic hydrocarbons " in 1972, the technical characterictic of disclosed catalyst is known in the document, and do not provide concrete preparation method, the preparation method who only mentions in an embodiment is an infusion process, preparation process comprises evaporation, drying, pulverizes, then with hydrogen reducing etc.And " known ruthenium catalyst and preparation method thereof is not the necessary part that he invents in the document " proposed clearly.European patent EP 0170915A2, among the embodiment that provides, the reaction time, the catalyst activity selectivity was not high mostly more than 3 hours.Chinese patent CN 1107757A ruthenium regenerating catalyst does not provide catalyst preparation technology.Benzene selective hydrogenation catalyst and catalysis technique up to now, worldwide, have only Japan to realize industrialization, and technical indicator is that benzene transforms at 40% o'clock, cyclohexene selectivity 80%.
The said adjustable sex change of the present invention is meant the pH value of utilizing the conditioned reaction system, and the activity of regulating catalyst and selectivity, purpose are to keep optionally stability of catalyst activity.About the adjustable sex change problem of ruthenium catalyst, do not see bibliographical information so far.
Recyclability is meant when the catalyst member inactivation, utilizes physics or chemical method, and its active selectivity is recovered, and purpose is to keep industrial continuity.
In the prior art, though have relate to catalyst regeneration, to different catalyst, because preparation method's difference, form differently, renovation process does not often have universality.As Chinese patent 94119103.6, ruthenium regenerating catalyst has provided a kind of renovation process of ruthenium catalyst, it is characterized in that to ruthenium catalyst wash, pickling or alkali cleaning, carry out reduction reaction then.Regeneration technology comprises two procedures, particularly reduces a step, makes troubles to commercial Application.And this regeneration techniques is that the applicant is at specific ruthenium catalyst.Other relevant ruthenium catalyst regeneration techniques does not appear in the newspapers.
Summary of the invention:
The purpose of this invention is to provide a kind of producing cyclohexene with benzene selective hydrogenation catalyst, a kind of method for preparing this catalyst is provided simultaneously with adjustable sex change and recyclability.Utilize this catalyst can realize the industrialization of producing cyclohexene with benzene selective hydrogenation, and integrated cost is low, the preparation process non-environmental-pollution.
The present invention also provides the modulating method and the renovation process of above-mentioned catalyst.
The present invention seeks to be achieved through the following technical solutions:
The producing cyclohexene with benzene selective hydrogenation catalyst is by active component Ru, rare-earth elements La or transition elements Zn or Fe, dispersant ZrO 2Form, it is characterized in that: each constituent mass percentage, Ru are ZrO 21-20%, La or Zn or Fe are the 0.1-10% of Ru.
During above-mentioned catalyst was formed, preferred Ru was ZrO 210-15%, La or Zn or Fe are the 1-5% of Ru.
The form that exists of active component Ru and rare-earth elements La or transition elements Zn or Fe is a metallic state, or hydroxide; Dispersant ZrO 2Be nanoscale.
Prepare the method for producing cyclohexene with benzene selective hydrogenation catalyst, the steps include:
A.RuCl 33H 2O is as the active component precursor, with LaCl 33H 2O is as the rare earth element precursor, or with FeSO 47H 2O or ZnSO 47H 2O, adds water and stirs into solution 1 in ratio given in the claim 1 as the transition elements precursor;
B. in solution 1, add dispersant ZrO in ratio given in the claim 1 2, stir 0.5-2h, become solution 2;
C. under stirring, press and RuCl 33H 2O+LaCl 33H 2O or and RuCl 33H 2O+FeSO 47H 2O or and RuCl 33H 2O+ZnSO 47H 2The quality of O is that 1: 1 ratio adds reducing agent NaBH in solution 2 4, Ru and La or Zn or Fe in the solution 2 are reduced to metallic state, standing demix, inclining supernatant liquor, keeps the slurries that lower floor contains solids, promptly gets product.
The another kind of method of preparation producing cyclohexene with benzene selective hydrogenation catalyst the steps include:
A. with RuCl 33H 2O is as the active component precursor, with LaCl 33H 2O is as the rare earth element precursor, or with FeSO 47H 2O or ZnSO 47H 2O, adds water and stirs into solution 1 in ratio given in the claim 1 as the transition elements precursor;
B. in solution 1, add dispersant ZrO in ratio given in the claim 1 2, stir 0.5-2h, become solution 2;
C. under stirring, press and RuCl 33H 2O+LaCl 33H 2O or and RuCl 33H 2O+FeSO 47H 2O or and RuCl 33H 2O+ZnSO 47H 2The mass ratio of O is that 1: 1.5 ratio adds precipitating reagent NaOH in solution 2, and Ru and La or Zn or Fe in the solution 2 are precipitated as hydroxide, standing demix, and inclining supernatant liquor, keeps the slurries that lower floor contains solids, promptly gets product.
The adjustable sex change of the alleged catalyst of the present invention is meant and utilizes the pH value that changes reaction system, the activity of regulating catalyst and selectivity.The reason that fluctuation takes place the catalyst activity selectivity changes relevant with the pH value of reacting slurry.In course of reaction, because product is constantly separated, simultaneously because water has certain solubility in organic facies, perhaps because operating condition improper often inevitably can cause moisture and ZnSO 4Loss, the pH value of reacting slurry changes, active selectivity fluctuates thereupon.Therefore modulation tech comprises the pH value of slurries in the monitoring course of reaction.When the pH value reduces, add rare H 2SO 4, when the pH value is too high, add Zn (OH) 2, the pH value of keeping reacting slurry is 4.0～5.0, and don't introduces new foreign ion.
The recyclability of the alleged catalyst of the present invention is meant when catalysqt deactivation, utilizes physics or chemical method, and its active selectivity is recovered.The main cause of catalysqt deactivation is its absorption to the slurries intermediate ion, so the technical scheme of catalyst regeneration is to be starting point with the ion that adsorbs on the flush away catalyst surface timely and effectively.
Above-mentioned producing cyclohexene with benzene selective hydrogenation catalyst activity and optionally modulating method be:
A. initial reaction stage, water benzene mass ratio is 1-4: 1-3 in the control reacting slurry, adds ZnSO 4The pH value of regulation and control reacting slurry is 4.6-5.0, ZnSO 4Concentration is 0.4-0.6moldm in slurries 3
B. in course of reaction, monitor the variation of slurry pH value.By adding rare H 2SO 4Or Zn (OH) 2, make the pH value of reacting slurry maintain 4.0-5.0.
Wherein: initial reaction stage, water benzene mass ratio is preferably 2: 1 in the control reacting slurry; ZnSO 4The concentration optimum is 0.5moldm in slurries 3, optimal pH is 4.85.
The renovation process of above-mentioned producing cyclohexene with benzene selective hydrogenation catalyst is:
A. use the pure water that contains the 1-3% hydrogen peroxide, the organic facies of flush away catalyst absorption;
B. use 0.3-1moldm 3Hydrochloric acid or sulfuric acid agitator treating 2-5 time, each 0.5-1.5h spends deionised water again to neutral.
Wherein: be used to wash best acid and be sulfuric acid, optimal concentration is 0.5moldm 3Best washing times is these 3 times; Best wash time is 1h.
Compared with prior art, the invention has the advantages that:
1, the invention provides a kind of novel Catalysts and its preparation method, integrated cost is low; Production process does not have discarded object, and non-environmental-pollution has actual industrial application value.
2, modulation is operated easily, and the regeneration condition gentleness not only can be kept the stability of production process, and can greatly prolong the service life of catalyst.
The specific embodiment:
Embodiment 1:
Take by weighing 2.8gRuCl 3NH 2O and 0.01gLaCl 3NH 2O is dissolved in an amount of distilled water, adds 6.5gZrO 2, stir 1h.Then with 2.8gNaBH 4Solution dropwise adds wherein, after question response is complete, continues to stir a period of time, makes Ru and La be reduced to metallic state, standing demix, and decant goes out supernatant liquor, keeps lower floor's black slurry liquid.Solid contents accounts for 20%, and slurry pH value is 8.
The gained catalyst is 7.5g, and wherein Ru is ZrO 210%, La is 1% of Ru.
Embodiment 2:
Take by weighing 3.5RuCl 3NH 2O and 0.03gLaCl 3NH 2O is dissolved in an amount of distilled water, adds 8gZrO 2, stir 1h.Then with 3.5gNaBH 4Solution dropwise adds wherein, after question response is complete, continues to stir a period of time, makes Ru and La be reduced to metallic state, standing demix, and decant goes out supernatant liquor, keeps lower floor's black slurry liquid.Solid contents accounts for 30%, and slurry pH value is 9.
The gained catalyst is 10g, and wherein Ru is ZrO 213%, La is 3% of Ru.
Embodiment 3:
Take by weighing 4.3gRuCl 3NH 2O and 0.05gLaCl 3NH 2O is dissolved in an amount of distilled water, adds 10gZrO 2, stir 1h.Then with 4.3gNaBH 4Solution dropwise adds wherein, after question response is complete, continues to stir a period of time, makes Ru and La be reduced to metallic state, standing demix, and decant goes out supernatant liquor, keeps lower floor's black slurry liquid.Solid contents accounts for 40%, and slurry pH value is 10.
The gained catalyst is 12g, and wherein Ru is ZrO 215%, La is 5% of Ru.
Embodiment 4:
Take by weighing 2.8RuCl 3NH 2O and 0.03gLaCl 3NH 2O is dissolved in an amount of distilled water, adds 6.5gZrO 2, stir 1h.Then 4.2gNaOH solution is dropwise added wherein, after question response is complete, continue to stir a period of time, make Ru and La be precipitated as hydroxide, standing demix, decant goes out supernatant liquor, keeps lower floor's black slurry liquid.Solid contents accounts for 20%, and slurry pH value is 8.
The gained catalyst is 8g, and wherein Ru is ZrO 210%, La is 1% of Ru.
Embodiment 5:
Take by weighing 3.5RuCl 3NH 2O and 0.03gLaCl 3NH 2O is dissolved in an amount of distilled water, adds 8gZrO 2, stir 1h.Then 5.2gNaOH solution is dropwise added wherein, after question response is complete, continue to stir a period of time, make Ru and La be precipitated as hydroxide, standing demix, decant goes out supernatant liquor, keeps lower floor's black slurry liquid.Solid contents accounts for 30%, and slurry pH value is 9.
The gained catalyst is 10g, and wherein Ru is ZrO 213%, La is 3% of Ru.
Embodiment 6:
Take by weighing 4.3gRuCl 3NH 2O and 0.05gLaCl 3NH 2O is dissolved in an amount of distilled water, adds 10gZrO 2, stir 1h.Then 6.5gNaOH solution is dropwise added wherein, after question response is complete, continue to stir a period of time, make Ru and La be precipitated as hydroxide, standing demix, decant goes out supernatant liquor, keeps lower floor's black slurry liquid.Solid contents accounts for 40%, and slurry pH value is 10.
The gained catalyst is 12g, and wherein Ru is ZrO 215%, La is 5% of Ru.
Embodiment 7:
Take by weighing 3.5RuCl 3NH 2O and 0.18gFeSO 47H 2O is dissolved in an amount of distilled water, adds 10ZrO 2, stir 1h.Then with 3.5gNaBH 4Solution dropwise adds wherein, after question response is complete, continues to stir a period of time, makes Ru and Fe be reduced to metallic state, standing demix, and decant goes out supernatant liquor, keeps lower floor's black slurry liquid.Solid contents accounts for 30%, and slurry pH value is 9.
The gained catalyst is 12g, and wherein Ru is ZrO 213%, Fe is 3% of Ru.
Embodiment 8:
Take by weighing 2.8gRuCl 3NH 2O and 0.05gFeSO 47H 2O is dissolved in an amount of distilled water, adds 10gZrO 2, stir 1h.Then 4.2gNaOH solution is dropwise added wherein, after question response is complete, continue to stir a period of time, make Ru and Fe be precipitated as hydroxide, standing demix, decant goes out supernatant liquor, keeps lower floor's black slurry liquid.Solid contents accounts for 20%, and slurry pH value is 8.
The gained catalyst is 11g, and wherein Ru is ZrO 210%, Fe is 1% of Ru
Embodiment 9:
Take by weighing 3.5RuCl 3NH 2O and 0.18gZnSO 47H 2O is dissolved in an amount of distilled water, adds 10gZrO 2, stir 1h.Then with 3.5gNaBH 4Solution dropwise adds wherein, after question response is complete, continues to stir a period of time, makes Ru and Zn be reduced to metallic state, standing demix, and decant goes out supernatant liquor, keeps lower floor's black slurry liquid.Solid contents accounts for 30%, and slurry pH value is 9.
The gained catalyst is 10g, and wherein Ru is ZrO 213%, Zn is 3% of Ru.
Embodiment 10:
Take by weighing 3.5RuCl 3NH 2O and 0.18gZnSO 47H 2O is dissolved in an amount of distilled water, adds 8gZrO 2, stir 1h.Then 5.2gNaOH solution is dropwise added wherein, after question response is complete, continue to stir a period of time, make Ru and Zn be precipitated as hydroxide, standing demix, decant goes out supernatant liquor, keeps lower floor's black slurry liquid.Solid contents accounts for 30%, and slurry pH value is 9.
The gained catalyst is 10g, and wherein Ru is ZrO 213%, Zn is 3% of Ru.
Activity of such catalysts, selective determination:
Choose embodiment 2 gained catalyst and carry out activity, selective determination, be determined in the minitype high voltage still and carry out.1 liter of autoclave, poly-tetrafluoro liner.Reaction system is a 280ml water, ZnSO 47H 2O 40.32g, solid contents 10g in the slurries, wherein Ru is 0.39g, all the other are the nanoscale zirconia.Begin to keep hydrogen pressure 4.0MPa then, stir 600r/min, 100 ℃/h of heating rate with air in the hydrogen exchange still.When treating that temperature rises to 140 ℃, preliminary treatment 8h..Add 140ml benzene then, pick up counting, regulate hydrogen pressure to 5MPa.Every the 5min sampling, gas chromatograph is analyzed benzene, cyclohexene, cyclohexane content in the oil phase, tries to achieve corresponding benzene conversion ratio and cyclohexene selectivity then.
Active selectivity is used γ respectively 40And S 40Expression: γ 40Be that benzene transforms at 40% o'clock, every gram catalyst per hour transforms the gram number of benzene, S 40Be that benzene transforms at 40% o'clock, the selectivity of cyclohexene.γ 40And S 40Acquisition, at first the time is mapped with the benzene conversion ratio, from scheming to determine that benzene transforms for 40% time, and the quality of Ru is brought following formula into and is calculated γ 40With the cyclohexene selectivity benzene conversion ratio is mapped again, determine that benzene transforms 40% o'clock cyclohexene selectivity S 40
γ 40 = V BZ ( ml ) × ρ BZ 0.88 × C BZ 0.4 t 40 ( h ) × W cat ( g )
In the formula, V BZRepresent the volume (ml) of benzene, ρ BzRepresent the density 0.88 of benzene, C BZBe benzene conversion ratio 0.4, t 40For benzene transforms for 40% time, represent W with h CatFor the quality of Ru in the solids, represent with g.
According to above-mentioned evaluation method, the activity of such catalysts selective data is listed in table 1.
Table 1. activity of such catalysts selective data
Reaction time/min benzene conversion ratio/% cyclohexene selection rate/% cyclohexene yield/%
5 7.70 91.46 7.04
15 22.61 88.66 20.05
30 39.95 84.71 33.84
45 54.73 80.91 44.28
60 66.75 76.75 51.23
According to top given γ 40And S 40Acquiring method, it is 30min that benzene transforms time of 40%, Ru is 0.39g, can get the γ of catalyst 40=252, S 40=84.6%.The industrial catalyst level is γ at present 40Greater than 100, S 40Be 80%.
Check modulation and regeneration effect are on the present catalyst activity of final body optionally changes.At first provide activity optionally condition determination and method below: minitype high voltage still, poly-tetrafluoro liner.Add 50ml water in the reaction system, 0.45 gram catalyst.With air in the hydrogen exchange still.Stir speed (S.S.) 600r/min.70 ℃/h of heating rate.Wait to be warming up to 135 ℃, do not carry out preliminary treatment, directly add 29ml benzene, hydrogen pressure transfers to 4.5MPa, and stir speed (S.S.) is increased to 1000r/min, and picks up counting.Benzene, cyclohexene, cyclohexane content in the gas chromatographic analysis oil phase, calculate the activity of such catalysts selectivity:
Active: benzene conversion ratio (C BZThe relative concentration of benzene * 100% in the)=product
Cyclohexene yield (Y HECyclohexene relative concentration * 100% in the)=product
Selectivity:
H 2SO 4To catalyst activity modulation situation optionally
Change ZnSO 47H 2The addition of O, active selectivity that can regulating catalyst.Zinc sulfate sees Table 2 to catalyst activity and selectivity modulation rule.
ZnSO in table 2. reacting slurry 4To catalyst activity selectivity modulation rule
Activity and selectivity when reacting 5min in the reacting slurry
Reacting slurry
ZnSO 4Concentration
PH value benzene conversion ratio/% cyclohexene selection rate/% cyclohexene yield/%
/mol·L -1
0.1 5.75 18.68 71.58 13.37
0.3 4.98 21.67 75.73 16.41
0.5 4.86 24.57 77.49 19.04
0.7 4.66 36.08 72.78 26.26
0.9 4.41 27.90 71.97 20.08
According to table 2 data, within the specific limits, with ZnSO 4The raising of concentration, reacting slurry pH value reduces.The conversion ratio of benzene raises.ZnSO in reacting slurry 4Concentration is 0.5moldm 3, the pH value of reacting slurry is 4.86, at this moment activity of such catalysts and selectivity the best.
Embodiment 11:Zn (OH) 2To catalyst activity of the present invention modulation optionally.
Water benzene mass ratio is 2: 1 in the control reacting slurry, adds ZnSO 4The pH value of regulation and control reacting slurry is 4.6-5.0, ZnSO 4Concentration is 0.4-0.6moldm in slurries 3Slurry pH value and catalyst activity selectivity situation of change in the tracing and monitoring reaction process.
If the pH value of reaction system is lower than 4.0, this moment, catalyst activity raise, and selectivity obviously reduces.Can add Zn (OH) 2, make it to raise.Add Zn (OH) 2Amount be to be advisable between 4～5 with the pH value of keeping slurries.
Table 3 is pH activity of such catalysts selective datas when on the low side:
Activity of such catalysts selective data (Ru is 0.39g) when table 3pH is on the low side
Reaction time/min benzene conversion ratio/% cyclohexene selection rate/% cyclohexene yield/%
5 21.22 81.94 17.39
15 54.82 72.46 39.72
30 81.64 58.86 48.05
45 92.77 46.37 43.02
60 97.33 34.85 33.92
Can be tried to achieve by data in the table 1, the time of benzene conversion 40% is 10.2min, the γ of catalyst 40=743, S 40=77.0%.
In order to reduce activity, improve selectivity, can add zinc hydroxide and carry out modulation, reduce activity, improve selectivity.Add 10ml 10 -3Zinc hydroxide after, activity of such catalysts is effectively suppressed, selectivity has then risen nearly 4 percentage points.The active selective data of zinc hydroxide modulation rear catalyst sees Table 4.
The active selective data of table 4 zinc hydroxide modulation rear catalyst
Reaction time/min benzene conversion ratio/% cyclohexene selection rate/% cyclohexene yield/%
5 10.33 88.19 9.11
15 29.59 84.06 24.87
30 52.99 78.13 41.40
45 69.65 72.19 50.28
60 80.75 66.49 53.69
Can be tried to achieve by data in the table 4, the time of benzene conversion 40% is 21.4min, and Ru is 0.39g, can get the γ of catalyst 40=354, S 40=81.6%.
This modulation has invertibity.If after the adding zinc hydroxide was excessive, activity was low excessively, available dilute sulfuric acid neutralizes, and recovers active.
Embodiment 12: adopt dilute sulfuric acid that catalyst is carried out modulation.
Water benzene mass ratio is 2: 1 in the control reacting slurry, adds ZnSO 4The pH value of regulation and control reacting slurry is 4.6-5.0, ZnSO 4Concentration is 0.4-0.6moldm in slurries 3Slurry pH value and catalyst activity selectivity situation of change in the tracing and monitoring reaction process.
If the pH value of reaction system is higher than 5.0, add 0.5moldm 3H 2SO 4, make it to reduce.Rare H 2SO 4Addition be to be to be advisable between 4～5 equally with the pH value of keeping slurries, corresponding pH value corresponding activity and selectivity accordingly.Corresponding relation sees Table 2.
Embodiment 13: catalyst regeneration
The regeneration foundation: the catalyst of his-and-hers watches inactivation absorbs with atom after with dissolving with hydrochloric acid to be analyzed, Zn concentration 3.32% in the catalyst, Fe concentration 0.78%, illustrate catalysqt deactivation be since in the solution Zn and reactor dissolve the absorption of Fe on catalyst of getting off and cause.
Renovation process:
Withdraw from 1/10th of catalyst at every turn and regenerate, in reaction system, add the raw catelyst of equivalent simultaneously, to keep the even running of reaction;
With the pure water that contains 1% hydrogen peroxide, the organic facies of flush away catalyst absorption, the pore structure of recovery catalyst;
Use 0.5moldm 3Hydrochloric acid agitator treating 3 times, each 1 hour, spend deionised water again to neutral, recover the composition and the surface nature of catalyst.Regeneration effect sees Table 5, the comparison between table 6 and the table 7.
The initial activity of catalyst sees Table 5:
The initial activity selective data of table 5. catalyst
Reaction time/min benzene conversion ratio/% cyclohexene selection rate/% cyclohexene yield/%
5 14.50 59.50 8.63
10 21.00 55.57 11.67
15 29.61 46.17 13.67
The active selective data of inactivation rear catalyst sees Table 6:
The active selective data of table 6. inactivation rear catalyst
Reaction time/min benzene conversion ratio/% cyclohexene selection rate/% cyclohexene yield/%
5 4.15 46.51 1.93
10 6.32 49.40 3.12
15 9.24 42.97 3.97
The active selective data of regeneration rear catalyst sees Table 7:
The active selective data of table 7. regeneration rear catalyst
Reaction time/min benzene conversion ratio/% cyclohexene selection rate/% cyclohexene yield/%
5 10.84 65.80 7.13
10 18.80 61.16 11.50
15 27.61 49.62 13.70
Regeneration effect: table 7 has provided the active selective data of regeneration rear catalyst.Comparison sheet 5 and table 7, as can be seen, active selectivity returns to the level of raw catelyst.

Claims (14)

1, producing cyclohexene with benzene selective hydrogenation catalyst is by active component Ru, rare-earth elements La or transition elements Zn or Fe, dispersant ZrO 2Form, it is characterized in that: each constituent mass percentage, Ru are ZrO 21-20%, La or Zn or Fe are the 0.1-10% of Ru.
2, according to the described producing cyclohexene with benzene selective hydrogenation catalyst of claim 1, it is characterized in that: preferred Ru is ZrO 210-15%, La or Zn or Fe are the 1-5% of Ru.
3, according to the described producing cyclohexene with benzene selective hydrogenation catalyst of claim 1, it is characterized in that: the form that exists of active component Ru and rare-earth elements La or transition elements Zn or Fe is a metallic state, or hydroxide.
4, according to claim 1 or 2 described producing cyclohexene with benzene selective hydrogenation catalyst, it is characterized in that: dispersant ZrO 2Be nanoscale.
5, prepare the method for producing cyclohexene with benzene selective hydrogenation catalyst, it is characterized in that:
A.RuCl 33H 2O is as the active component precursor, with LaCl 33H 2O is as the rare earth element precursor, or with FeSO 47H 2O or ZnSO 47H 2O, adds water and stirs into solution 1 in ratio given in the claim 1 as the transition elements precursor;
B. in solution 1, add dispersant ZrO in ratio given in the claim 1 2, stir 0.5-2h, become solution 2;
C. under stirring, press and RuCl 33H 2O+LaCl 33H 2O or and RuCl 33H 2O+FeSO 47H 2O or and RuCl 33H 2O+ZnSO 47H 2The quality of O is that 1: 1 ratio adds reducing agent NaBH in solution 2 4, Ru and La or Zn or Fe in the solution 2 are reduced to metallic state, standing demix, inclining supernatant liquor, keeps the slurries that lower floor contains solids, promptly gets product.
6, prepare the method for producing cyclohexene with benzene selective hydrogenation catalyst, it is characterized in that:
A. with RuCl 33H 2O is as the active component precursor, with LaCl 33H 2O is as the rare earth element precursor, or with FeSO 47H 2O or ZnSO 47H 2O, adds water and stirs into solution 1 in ratio given in the claim 1 as the transition elements precursor;
B. in solution 1, add dispersant ZrO in ratio given in the claim 1 2, stir 0.5-2h, become solution 2;
C. under stirring, press and RuCl 33H 2O+LaCl 33H 2O or and RuCl 33H 2O+FeSO 47H 2O or and RuCl 33H 2O+ZnSO 47H 2The mass ratio of O is that 1: 1.5 ratio adds precipitating reagent NaOH in solution 2, and Ru and La or Zn or Fe in the solution 2 are precipitated as hydroxide, standing demix, and inclining supernatant liquor, keeps the slurries that lower floor contains solids, promptly gets product.
7, the modulating method of the described producing cyclohexene with benzene selective hydrogenation catalyst of claim 1 is characterized in that:
A. initial reaction stage, water benzene mass ratio is 1-4: 1-3 in the control reacting slurry, adds ZnSO 4The pH value of regulation and control reacting slurry is 4.6-5.0, ZnSO 4Concentration is 0.4-0.6moldm in slurries 3
B. in course of reaction, monitor the variation of slurry pH value.By adding rare H 2SO 4Or Zn (OH) 2, make the pH value of reacting slurry maintain 4.0-5.0.
8, according to the modulating method of the described producing cyclohexene with benzene selective hydrogenation catalyst of claim 7, it is characterized in that: initial reaction stage, water benzene mass ratio is preferably 2: 1 in the control reacting slurry.
9, according to the modulating method of the described producing cyclohexene with benzene selective hydrogenation catalyst of claim 7, it is characterized in that: pH value the best of reacting slurry is 4.85.
10, according to the modulating method of the described producing cyclohexene with benzene selective hydrogenation catalyst of claim 7, it is characterized in that: ZnSO 4The concentration optimum is 0.5moldm in slurries 3
11, the renovation process of the described producing cyclohexene with benzene selective hydrogenation catalyst of claim 1 is characterized in that:
A. use the pure water that contains the 1-3% hydrogen peroxide, the organic facies of flush away catalyst absorption;
B. use 0.3-1moldm 3Hydrochloric acid or sulfuric acid agitator treating 2-5 time, each 0.5-1.5h spends deionised water again to neutral.
12, according to the renovation process of the described producing cyclohexene with benzene selective hydrogenation catalyst of claim 10, it is characterized in that: be used to wash best acid and be sulfuric acid, optimal concentration is 0.5moldm 3
13, according to the renovation process of the described producing cyclohexene with benzene selective hydrogenation catalyst of claim 10, it is characterized in that: best washing times is these 3 times
14, according to the renovation process of the described producing cyclohexene with benzene selective hydrogenation catalyst of claim 10, it is characterized in that: best wash time is 1h.
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CN102989521A (en) * 2012-12-17 2013-03-27 中国科学院大连化学物理研究所 Zirconium-containing spinel supported honeycomb monolithic catalyst for selective hydrogenation of benzene and preparation method for same
CN105056971A (en) * 2015-08-07 2015-11-18 郑州大学 In-situ regeneration method of Ru-Zn catalyst for preparation of cyclohexene by benzene selective hydrogenation
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CN115259992A (en) * 2022-08-12 2022-11-01 内蒙古庆华集团腾格里精细化工有限公司 Continuous production method for preparing cyclohexene by benzene selective hydrogenation

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CN101269326B (en) * 2007-03-21 2010-05-19 中国科学院大连化学物理研究所 Integral catalyst for producing cyclohexene with benzene hydrogenation and method for producing the same
CN102989521A (en) * 2012-12-17 2013-03-27 中国科学院大连化学物理研究所 Zirconium-containing spinel supported honeycomb monolithic catalyst for selective hydrogenation of benzene and preparation method for same
CN102989521B (en) * 2012-12-17 2015-03-04 中国科学院大连化学物理研究所 Zirconium-containing spinel supported honeycomb monolithic catalyst for selective hydrogenation of benzene and preparation method for same
CN105056971A (en) * 2015-08-07 2015-11-18 郑州大学 In-situ regeneration method of Ru-Zn catalyst for preparation of cyclohexene by benzene selective hydrogenation
CN105130734A (en) * 2015-08-07 2015-12-09 郑州大学 Activity selectivity modulating method of Ru-Zn catalyst for cyclohexene production through benzene selective hydrogenation
CN115259992A (en) * 2022-08-12 2022-11-01 内蒙古庆华集团腾格里精细化工有限公司 Continuous production method for preparing cyclohexene by benzene selective hydrogenation
CN115259992B (en) * 2022-08-12 2023-11-28 内蒙古庆华集团腾格里精细化工有限公司 Continuous production method for preparing cyclohexene by benzene selective hydrogenation

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