CN107626306A - A kind of preparation method of mononuclear aromatics partial hydrogenation catalyst - Google Patents
A kind of preparation method of mononuclear aromatics partial hydrogenation catalyst Download PDFInfo
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- CN107626306A CN107626306A CN201710755886.4A CN201710755886A CN107626306A CN 107626306 A CN107626306 A CN 107626306A CN 201710755886 A CN201710755886 A CN 201710755886A CN 107626306 A CN107626306 A CN 107626306A
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- ruthenium
- zinc
- partial hydrogenation
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- hydrogenation catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000005406 washing Methods 0.000 claims abstract description 19
- QORYBJZFIBBDSH-UHFFFAOYSA-N ruthenium zinc Chemical compound [Zn].[Zn].[Zn].[Ru] QORYBJZFIBBDSH-UHFFFAOYSA-N 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 140
- 239000000243 solution Substances 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000004062 sedimentation Methods 0.000 claims description 27
- 150000003303 ruthenium Chemical class 0.000 claims description 24
- 239000006228 supernatant Substances 0.000 claims description 24
- 150000003751 zinc Chemical class 0.000 claims description 23
- 239000000725 suspension Substances 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000003643 water by type Substances 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 12
- 238000006073 displacement reaction Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 6
- 239000000284 extract Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical class O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 claims description 6
- 235000005074 zinc chloride Nutrition 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- -1 ruthenium halide Chemical class 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000013618 particulate matter Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- 239000000843 powder Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000005070 sampling Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001925 cycloalkenes Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VDRDGQXTSLSKKY-UHFFFAOYSA-K ruthenium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ru+3] VDRDGQXTSLSKKY-UHFFFAOYSA-K 0.000 description 2
- WQGCFAUZCZTVDM-UHFFFAOYSA-H ruthenium(3+);trisulfate Chemical class [Ru+3].[Ru+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O WQGCFAUZCZTVDM-UHFFFAOYSA-H 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- AVAYXTKDRHARSR-UHFFFAOYSA-N [Zn].[Ru] Chemical compound [Zn].[Ru] AVAYXTKDRHARSR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical class [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
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Abstract
The invention discloses a kind of preparation method of mononuclear aromatics partial hydrogenation catalyst, belong to catalyst technical field.This preparation method comprises the following steps：(1) ruthenium zinc solution is prepared；(2) it is co-precipitated；(3) once washing；(4) reduce；(5) secondary washing.The preparation method of mononuclear aromatics partial hydrogenation catalyst of the present invention is than catalyst high income prepared by prior art, and cost is low, and catalyst activity is high and more stable.
Description
Technical field
The present invention relates to a kind of preparation method of mononuclear aromatics partial hydrogenation catalyst, belong to catalyst technical field.
Background technology
Mononuclear aromatics can partial hydrogenation manufacture cycloolefin, cycloolefin (such as cyclohexene) is important industrial chemicals,
There are multiple patents, as CN1676215A, CN02814607.7, CN102264471, CN1533375A, CN102125841A, JP are special
Open the preparation method that 2000-26322 (P2000-26322A) discloses its catalyst：1) first it is added in ruthenium zinc salt and is precipitated with alkali
Go out the hydroxide of ruthenium, zinc, 2) wash again or do not wash out accessory substance salinity, obtain black solid, 3) adjustment pH value, add
Or be added without carrier and reduce to obtain black solid, its average grain diameter is within 20 nanometers.
The content of the invention
Applicant of the present invention has found that under same control condition, reaction sampling is quiet doing among partial hydrogenation of benzene research
Black floccule occurs in the oil-water interfaces put, sometimes more, sometimes few.Applicant after research by having found, prior art
For obtained catalyst after catalysis mononuclear aromatics reaction, the floccule of oil-water interfaces black occurs in water-oil separating for material,
This causes catalyst loss to increase.Applicant's analysis is found, manufactures the co-precipitation of aromatic moiety hydrogenation catalyst in the prior art
Step is all the reaction method being added dropwise using alkali lye into ruthenium salt, zinc salt compound solution, and this operation may result in one
Problem, i.e., with system alkali gradually increase, precipitation system is one by alkali or OH-It is insufficient gradually to equivalent or excess
Course of reaction；Different insoluble matters has different solubility product constant value Ksp, crystal zinc hydroxide Ksp values 1.2 × 10 in water-17,
Its amorphous substance Ksp values are 2.09 × 10-16, hydroxide ruthenium Ksp values are 1.0 × 10-36, contrast both Ksp values and can be seen that
When alkali is in shortage, it is intended to the preferential reaction of hydroxide ruthenium；With the generation of precipitation, the pH of solution is a gradual increased mistake
Journey, this precipitation ruthenium zinc ratio that can be resulted in constantly change, the Ruthenium of the more deuterogenic precipitation of precipitation of initial reaction stage generation
Zinc ratio is different, and this can influence the homogeneity/stability for precipitating grain fraction；Using when catalyst be and ZrO2Common suspend is divided
Dissipate the catalytic benzene hydrogenation in solution of zinc sulfate to react, oil-water interfaces take away more catalysis when the unstable catalyst of component separates
Agent active component.
In addition, for commercial object, the method using least cost is always tried hard to for a technology people, makes great efforts to make
More practical product.Exactly basis is improved the application herein, it is therefore an objective to improves the stability of catalyst.The present invention is improved
Method And Principle is to ensure during precipitation reaction OH in reaction solution-It is excessive or enough, ensure zinc, the synchronism of ruthenium precipitation, this
Sample ensures the homogeneity of precipitation, stability.
Present invention aims to solve the deficiencies of the prior art, and provides a kind of a kind of preparation of mononuclear aromatics partial hydrogenation catalyst
Method.The present invention is than catalyst high income prepared by prior art, and cost is low, and catalyst activity is high and more stable.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：A kind of preparation of mononuclear aromatics partial hydrogenation catalyst
Method, comprise the following steps：
(1) ruthenium zinc solution is prepared：Ruthenium salt that 0.11mol is solvable and the solvable zinc salts of 0.018-0.0415mol are taken, under normal pressure
It is dissolved in 20-80 DEG C in 5.5-22mol deionized waters, obtains the mixed solution of ruthenium salt and zinc salt；
(2) it is co-precipitated：Take 0.5-0.875molNaOH solids to be dissolved in 100-700ml deionized water, be heated to 70-
110 DEG C, the NaOH solution after being heated, the ruthenium salt and the mixed solution of zinc salt that step (1) is obtained, it is gradually added under normal pressure
It is stirring while adding in NaOH solution after to above-mentioned heating, until no longer producing precipitation, then at 50-92 DEG C of continuation insulated and stirred
0-10h, obtain suspension；
(3) once washing：The suspension centrifugal sedimentation that step (2) is obtained, abandoning supernatant, black mud is obtained, will
150-200ml 0.1-1mol/L NaOH solution is added in above-mentioned black mud, centrifugal sedimentation, abandoning supernatant, is obtained
Black mud；
150-200ml 0.1-1mol/L NaOH solution is added in above-mentioned black mud again, centrifugal sedimentation, discarded
Supernatant, black mud is obtained, is repeated the above steps 2-5 times altogether, the black mud after being washed；
(4) reduce：Black mud after step (3) is washed is diluted to suspended with the water of 1.5-5 times of mud weight
Liquid, regulation pH value are 13-14, are added in autoclave, first with nitrogen displacement, then are replaced with hydrogen, pressurizeed, high-speed stirred
Afterwards, in 80-150 DEG C of heat-insulation pressure keeping 2-36h；
(5) secondary washing：Autoclave is naturally cooling to 20-25 DEG C, kettle liquid is extracted out, with distilled water or pure water
It is 7-9 to pH value, obtains particulate matter, as mononuclear aromatics partial hydrogenation catalyst.
On the basis of above-mentioned technical proposal, the present invention can also do following improvement.
Further, in step (1), the solvable ruthenium salt is halide, nitrate or the sulfate of ruthenium, described solvable
Zinc salt be zinc halide, nitrate or sulfate.
Further, the halide of the ruthenium is three hydrate ruthenium trichlorides, and the halide of the zinc is zinc chloride.
Further, in step (2), the reaction vessel of the co-precipitation is beaker, flask or reactor.
Further, in step (3), the time of the centrifugal sedimentation is 1-15min, and rotating speed is 750-3000rpm.
It is using above-mentioned further beneficial effect：Compared with natural sedimentation high income, and water-saving is time saving.
Further, in step (4), the pressure of the pressurization is 1-7Mpa, and the temperature during high-speed stirred is 80-
150 DEG C, speed 1000-2000rpm, time 2-36h.
The beneficial effects of the invention are as follows：
1. the catalyst prepared by the present invention, when being reacted for catalyzing aromatic hydrocarbon partial hydrogenation, compared to the prior art, protecting
Under conditions of demonstrate,proving yield, the layering of reaction solution profit improves substantially, advantageously reduces catalyst consumption in production, reduces catalyst and disappears
Consume cost.
2. catalyst component prepared by the present invention is homogeneous, component is stable, activity is relatively high and stable.
3. the preparation method of the present invention is simple, wide market, it is adapted to large-scale production.
Brief description of the drawings
Fig. 1 is catalyst sampling oil-water separation figure prepared by the embodiment of the present invention 1, wherein, 1 is upper oil phase, and 2 are
Interface, 3 be catalyst and water mixed phase.
Fig. 2 is catalyst sampling oil-water separation figure prepared by comparative example 1 of the present invention, wherein, 1 is upper oil phase, and 2 are
Interface, 3 be catalyst and water mixed phase.
Embodiment
The principle and feature of the present invention are described below in conjunction with specific accompanying drawing, example is served only for explaining this hair
It is bright, it is not intended to limit the scope of the present invention.
Embodiment 1
The preparation method of the mononuclear aromatics partial hydrogenation catalyst of the present embodiment, comprises the following steps：
(1) ruthenium zinc solution is prepared：The hydrate ruthenium trichlorides of 0.11mol tri- and 0.03676mol zinc chloride are taken, in 60 under normal pressure
DEG C it is dissolved in 240ml deionized waters, obtains the mixed solution of ruthenium salt and zinc salt；
(2) it is co-precipitated：Take 0.75mol NaOH solids to be placed in tri- mouthfuls of reaction bulbs of 500ml, add 140ml deionized waters, add
Heat is to 110 DEG C, the NaOH solution after being heated, the ruthenium salt and the mixed solution of zinc salt that step (1) is obtained, under normal pressure gradually
It is added in the NaOH solution after above-mentioned heating, it is stirring while adding, drip off within 25 minutes, continue insulated and stirred 2.5h then at 50 DEG C,
Obtain suspension；
(3) once washing：The suspension that step (2) obtains is poured into 300ml centrifuge tubes, 750rpm centrifugal sedimentations
15min, abandoning supernatant, black mud is obtained, 200mL 0.1mol/L NaOH solution is added to above-mentioned black mud
In, 1500rpm centrifugal sedimentation 5min, abandoning supernatant, obtain black mud；
200mL 0.1mol/L NaOH solution is added in above-mentioned black mud again, 750rpm centrifugal sedimentation 5min,
Abandoning supernatant, obtain black mud；Repeat the above steps altogether 2 times, the black mud after being washed；
(4) reduce：Black mud after step (3) is washed is diluted to outstanding with the deionized water of 3 times of mud weights
Turbid, it is 13 with NaOH solution regulation pH value, is added in autoclave, first with nitrogen displacement, then is replaced with hydrogen, pressurizeed
To 4MPa, in 140 DEG C, 1000rpm high-speed stirreds simultaneously stir and heat by pressurize 12h, afterwards stopping；
(5) secondary washing：Autoclave is naturally cooling to 20 DEG C, extracts kettle liquid out, being washed with distilled water to pH value is
7, by vacuum drying, obtain 10.8g particulate matters, as mononuclear aromatics partial hydrogenation catalyst.
The catalyst being prepared is subjected to activity rating, the results are shown in Table 1.The catalyst being prepared is sampled and stood,
Profit boundary is as shown in Figure 1.
Embodiment 2
The preparation method of the mononuclear aromatics partial hydrogenation catalyst of the present embodiment, comprises the following steps：
(1) ruthenium zinc solution is prepared：The hydrate ruthenium trichlorides of 0.0729mol tri- and 0.0214mol zinc chloride are taken, in 78 under normal pressure
DEG C it is dissolved in 240ml deionized waters, obtains the mixed solution of ruthenium salt and zinc salt；
(2) it is co-precipitated：Take 0.525mol NaOH to be placed in 500ml beakers, add 110ml deionized waters, be heated to 80
DEG C, the NaOH solution after being heated, the ruthenium salt and the mixed solution of zinc salt that step (1) is obtained, it is added gradually under normal pressure
It is stirring while adding in NaOH solution after above-mentioned heating, drip off within 35 minutes, until no longer producing precipitation, continue to protect then at 80 DEG C
Temperature stirring 2.5h, obtains suspension；
(3) once washing：The suspension that step (2) obtains is poured into 300ml centrifuge tubes, 2000rpm centrifugal sedimentations
8min, abandoning supernatant, black mud is obtained, 180mL 0.5mol/L NaOH solution is added in above-mentioned black mud,
2000rpm centrifugal sedimentation 3min, abandoning supernatant, obtain black mud；
180mL 0.5mol/L NaOH solution is added in above-mentioned black mud again, 1500rpm centrifugal sedimentations
3min, abandoning supernatant, the black mud after being washed；
(4) reduce：Black mud after step (3) is washed with plus 1.5 times of mud weights water be diluted to it is suspended
Liquid, it is 13 with NaOH solution regulation pH value, is added in autoclave, first with nitrogen displacement, then uses H2Displacement, is forced into
4MPa and pressurize, in 145 DEG C, 1200rpm high-speed stirred 19h, stop stirring and heating afterwards；
(5) secondary washing：Autoclave is naturally cooling to 22 DEG C, extracts kettle liquid out, is 8 with pure water to pH value,
By vacuum drying, 7.2g particulate matters, as mononuclear aromatics partial hydrogenation catalyst are obtained.
The catalyst being prepared is subjected to activity rating, the results are shown in Table 1.
Embodiment 3
The preparation method of the mononuclear aromatics partial hydrogenation catalyst of the present embodiment, comprises the following steps：
(1) ruthenium zinc solution is prepared：0.0732mol ruthenium sulfates and 0.0325mol zinc nitrates are taken, is dissolved under normal pressure in 20 DEG C
In 200ml deionized waters, the mixed solution of ruthenium salt and zinc salt is obtained；
(2) it is co-precipitated：Take 0.605mol NaOH to be placed in 500ml reactors, add 110ml deionized waters, be heated to 92
DEG C, the NaOH solution after being heated, the ruthenium salt and the mixed solution of zinc salt that step (1) is obtained, it is added gradually under normal pressure
It is stirring while adding in NaOH solution after above-mentioned heating, drip off within 29 minutes, until no longer producing precipitation, continue to protect then at 92 DEG C
Temperature stirring 3.5h, obtains suspension；
(3) once washing：The suspension that step (2) obtains is poured into 300ml centrifuge tubes, 3000rpm centrifugal sedimentations
1min, abandoning supernatant, black mud is obtained, 150mL 1mol/L NaOH solution is added in above-mentioned black mud,
3000rpm centrifugal sedimentation 1min, abandoning supernatant, obtain black mud；
150mL 1mol/L NaOH solution is added in above-mentioned black mud again, 1100rpm centrifugal sedimentation 1min,
Abandoning supernatant, obtain black mud；Repeat the above steps altogether 5 times, the black mud after being washed；
(4) reduce：Black mud after step (3) is washed is diluted to suspension with the water of 5 times of mud weights, uses
NaOH solution regulation pH value is 13-14, is added in autoclave, first with nitrogen displacement, then uses H2Displacement, is forced into 7Mpa
And pressurize, in 150 DEG C, 1000rpm high-speed stirred 2h, stop stirring and heating afterwards；
(5) secondary washing：Autoclave is naturally cooling to 25 DEG C, kettle liquid is extracted out, is with pure water to pH value
9, by vacuum drying, obtain 7.3g particulate matters, as mononuclear aromatics partial hydrogenation catalyst.
The catalyst being prepared is subjected to activity rating, the results are shown in Table 1.
Embodiment 4
The preparation method of the mononuclear aromatics partial hydrogenation catalyst of the present embodiment, comprises the following steps：
(1) ruthenium zinc solution is prepared：The hydrate ruthenium trichlorides of 0.1138mol tri- and 0.0338mol zinc chloride are taken, in 30 under normal pressure
DEG C it is dissolved in 400ml deionized waters, obtains the mixed solution of ruthenium salt and zinc salt；
(2) it is co-precipitated：Take 0.8055mol NaOH to be placed in tri- mouthfuls of reaction bulbs of 1000ml, add 100ml deionized waters, heating
To 70 DEG C, the NaOH solution after being heated, the ruthenium salt and the mixed solution of zinc salt that step (1) is obtained, under normal pressure gradually plus
Enter into the NaOH solution after above-mentioned heating, it is stirring while adding, drip off within 29 minutes, until no longer producing precipitation, then at 70 DEG C after
Continuous insulated and stirred 2h, obtains suspension；
(3) suspension that step (2) obtains is poured into 300ml centrifuge tubes, 1500rpm centrifugal sedimentation 10min, discarded
Supernatant, obtain black mud, 160mL 0.6mol/L NaOH solution be added in above-mentioned black mud, 1500rpm from
The heart settles 4min, abandoning supernatant, obtains black mud；
160mL 0.6mol/L NaOH solution is added in above-mentioned black mud again, 1500rpm centrifugal sedimentations
10min, abandoning supernatant, obtain black mud；Repeat the above steps altogether 3 times, the black mud after being washed；
(4) reduce：Black mud after step (3) is washed is diluted to suspension with the water of 5 times of mud weights, uses
NaOH solution regulation pH value is 13.3, is added in autoclave, first with nitrogen displacement, then is replaced with hydrogen, is forced into
3Mpa and pressurize, in 140 DEG C, 1200rpm high-speed stirred 20h, stop stirring and heating afterwards；
(5) secondary washing：Autoclave is naturally cooling to 20 DEG C, extracts kettle liquid out, is 7 with pure water to pH value,
By vacuum drying, 11.0g particulate matters, as mononuclear aromatics partial hydrogenation catalyst are obtained.
The catalyst being prepared is subjected to activity rating, the results are shown in Table 1.
Embodiment 5
The preparation method of the mononuclear aromatics partial hydrogenation catalyst of the present embodiment, comprises the following steps：
(1) ruthenium zinc solution is prepared：0.1103mol ruthenium sulfates and 0.0362mol zinc sulfate are taken, is dissolved under normal pressure in 80 DEG C
In 150ml deionized waters, the mixed solution of ruthenium salt and zinc salt is obtained；
(2) it is co-precipitated：Take 0.8805mol NaOH to be placed in 1000ml beakers, add 600ml deionized waters, be heated to
102 DEG C, the NaOH solution after being heated, the ruthenium salt and the mixed solution of zinc salt that step (1) is obtained, it is gradually added under normal pressure
It is stirring while adding in NaOH solution after to above-mentioned heating, drip off within 10 minutes, then at 70 DEG C of continuation insulated and stirred 0.2h, obtain
Suspension；
(3) once washing：The suspension that step (2) obtains is poured into 300ml centrifuge tubes, 1000rpm centrifugal sedimentations
12min, abandoning supernatant, black mud is obtained, 170mL 0.3mol/L NaOH solution is added to above-mentioned black mud
In, 1000rpm centrifugal sedimentation 12min, abandoning supernatant, obtain black mud；
170mL 0.3mol/L NaOH solution is added in above-mentioned black mud again, 1000rpm centrifugal sedimentations
12min, abandoning supernatant, obtain black mud；Repeat the above steps altogether 2 times, the black mud after being washed；
(4) reduce：Black mud after step (3) is washed is diluted to suspension with the water of 1.5 times of mud weights,
It is 13-14 with NaOH solution regulation pH value, is added in autoclave, first with nitrogen displacement, then is replaced with H2, be forced into
5MPa, in 120 DEG C, 1300rpm high-speed stirreds 25h, 145 DEG C of heat-insulation pressure keeping 10h, stop stirring and heating afterwards；
(5) secondary washing：Autoclave is naturally cooling to 21 DEG C, extracts kettle liquid out, is 9 with pure water to pH value,
By vacuum drying, 11.0g particulate matters, as mononuclear aromatics partial hydrogenation catalyst are obtained.
The catalyst being prepared is subjected to activity rating, the results are shown in Table 1.
Embodiment 6
The preparation method of the mononuclear aromatics partial hydrogenation catalyst of the present embodiment, comprises the following steps：
(1) ruthenium zinc solution is prepared：The hydrate ruthenium trichlorides of 0.0384mol tri- and 0.0156mol zinc chloride are taken, in 20 under normal pressure
DEG C it is dissolved in 50ml deionized waters, obtains the mixed solution of ruthenium salt and zinc salt；
(2) it is co-precipitated：0.2503molNaOH is placed in 500ml reactors, is added 350ml deionized waters, is heated to 80
DEG C, the NaOH solution after being heated, the ruthenium salt and the mixed solution of zinc salt that step (1) is obtained, it is added gradually under normal pressure
It is stirring while adding in NaOH solution after above-mentioned heating, drip off within 10 minutes, obtain suspension；
(3) once washing：The suspension that step (2) obtains is poured into 300ml centrifuge tubes, 1200rpm centrifugal sedimentations
11min, abandoning supernatant, black mud is obtained, 100mL 0.7mol/L NaOH solution is added to above-mentioned black mud
In, 1200rpm centrifugal sedimentation 11min, abandoning supernatant, obtain black mud；
190mL 0.7mol/L NaOH solution is added in above-mentioned black mud again, 1200rpm centrifugal sedimentations
11min, abandoning supernatant, obtain black mud；Repeat the above steps altogether 3 times, the black mud after being washed；
(4) reduce：Black mud after step (3) is washed is diluted to suspension with the water of 5 times of mud weights, uses
NaOH solution regulation pH value is 13-14, is added in autoclave, first with nitrogen displacement, then is replaced with hydrogen, is forced into
1Mpa and pressurize, in 80 DEG C, 1300rpm high-speed stirreds, heat-insulation pressure keeping 36h, stop heating, stirring afterwards；
(5) secondary washing：Autoclave is naturally cooling to 24 DEG C, extracts kettle liquid out, being washed with distilled water to pH value is
9, by vacuum drying, obtain 3.5g particulate matters, as mononuclear aromatics partial hydrogenation catalyst.
The catalyst being prepared is subjected to activity rating, the results are shown in Table 1.
Comparative example 1
Preparation method reference embodiment 2, unlike, in step (2), reaction mass dropwise addition order is different, will obtain
Heating after NaOH solution be added in the mixed solution of ruthenium salt that step (1) obtains and zinc salt, it is other same as Example 2,
Obtain 3.6g black solid powder.Take above-mentioned black solid powder to carry out activity rating, the results are shown in Table 1.By above-mentioned black solid
Powder agent sampling is stood, and profit boundary is as shown in Figure 2.
Comparative example 2
Preparation method reference embodiment 4, unlike, in step (2), reaction mass dropwise addition order is different, will obtain
Heating after NaOH solution be added in the mixed solution of ruthenium salt that step (1) obtains and zinc salt；Sunk in step (3) using nature
Drop washing black mud, sinking speed is slow, takes 10h；It is other same as Example 4, obtain 3.5g black solid powder.Take
State black solid powder and carry out catalyst progress activity rating, the results are shown in Table 1.
Comparative example 3
Preparation method reference embodiment 6, unlike, in step (2), reaction mass dropwise addition order is different, will obtain
Heating after NaOH solution be added in the mixed solution of ruthenium salt that step (1) obtains and zinc salt, it is other same as Example 6,
Obtain 3.6g black solid powder.Above-mentioned black solid powder is subjected to activity rating, the results are shown in Table 1.
Activity rating and computational methods
The catalyst for taking 1.96g embodiments 1-6, comparative example 1-3 to be prepared respectively, respectively with 10g ZrO2(average grain
Footpath 0.1um), 49g white vitriols, 280g water be added to together in the 1L autoclave of Hastelloy liner, hydrogen displacement
After be pressurized to 4MPa sealings, stir 1000rpm and be warming up to 140 DEG C, high-speed stirred pressurize 24h, be then warming up to 145 DEG C, let out
3MPa, high-speed stirred are pressed onto, then 140ml purified petroleum benzin H2After being pressed into reactor, H is used rapidly2Pressurize and be maintained to reactor
5MPa, 142 ± 2 DEG C of controlling reaction temperature, periodically negated with 50ml volumetric flasks and answer oil, water catalyst aggregate sample in 12min kettles, used
Gas chromatographic analysis oil phase, while how much observe and record oil-water interfaces attached catalyst, such as adhere to more dark colored powder, then judge
The catalyst is lost in when easily water-oil separating operates in production with oil phase.
Evaluation response formula：
Benzene+H2=hexamethylene+cyclohexene
The calculating (molal quantity is used in formula) of activity：
The Activity evaluation of catalyst prepared by the embodiment 1-6 of table 1 and comparative example 1-3
From table 1, catalyst prepared by the present invention is compared with catalyst prepared by contrast test, prepared by same formula
Do not lose active, selectivity it is slightly higher on the premise of, the catalyst for preparing of the present invention has preferable stability, not easily runs off.
As seen from Figure 1, the catalyst sampling that prepared by the present invention is stood, and profit boundary is substantially without catalyst.Can by Fig. 2
See, the catalyst sampling of comparative example is stood, and profit boundary entrained catalyst is more.
As can be seen here, method of the invention, under conditions of yield is ensured, the layering of reaction solution profit improves substantially, favorably
In reducing catalyst consumption in production, catalyst consumption cost is reduced, and catalyst component is homogeneous, component is stable, activity is higher
And stably.
In addition, step (3) centrifugal sedimentation 1-15min can fully be settled out black mud, and mud moisture content is low, washing effect
Rate is much higher than natural subsidence, this explanation centrifugal process can water-saving it is time saving.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.
Claims (6)
1. a kind of preparation method of mononuclear aromatics partial hydrogenation catalyst, it is characterised in that comprise the following steps：
(1) ruthenium zinc solution is prepared：Take ruthenium salt that 0.11mol is solvable and the solvable zinc salts of 0.018-0.0415mol, under normal pressure in
20-80 DEG C is dissolved in 5.5-22mol deionized waters, obtains the mixed solution of ruthenium salt and zinc salt；
(2) it is co-precipitated：Take 0.5-0.875molNaOH solids to be dissolved in 100-700ml deionized water, be heated to 70-110 DEG C,
NaOH solution after being heated, the ruthenium salt and the mixed solution of zinc salt that step (1) is obtained, it is added gradually under normal pressure above-mentioned
It is stirring while adding in NaOH solution after heating, until no longer producing precipitation, continue insulated and stirred 0-10h then at 50-92 DEG C,
Obtain suspension；
(3) once washing：The suspension centrifugal sedimentation that step (2) is obtained, abandoning supernatant, obtains black mud, by 150-
200ml 0.1-1mol/L NaOH solution is added in above-mentioned black mud, centrifugal sedimentation, abandoning supernatant, obtains black
Mud；
150-200ml 0.1-1mol/L NaOH solution is added in above-mentioned black mud again, centrifugal sedimentation, supernatant discarding
Liquid, black mud is obtained, is repeated the above steps 2-5 times altogether, the black mud after being washed；
(4) reduce：Black mud after step (3) is washed is diluted to suspension with the water of 1.5-5 times of mud weight, adjusts
Section pH value is 13-14, is added in autoclave, first with nitrogen displacement, then is replaced with hydrogen, pressurizeed, after high-speed stirred, in
80-150 DEG C of heat-insulation pressure keeping 2-36h；
(5) secondary washing：Autoclave is naturally cooling to 20-25 DEG C, extracts kettle liquid out, with distilled water or pure water to pH
It is worth for 7-9, obtains particulate matter, as mononuclear aromatics partial hydrogenation catalyst.
2. the preparation method of a kind of mononuclear aromatics partial hydrogenation catalyst according to claim 1, it is characterised in that in step
Suddenly in (1), the solvable ruthenium salt be ruthenium halide, nitrate or sulfate, the solvable zinc salt for zinc halide,
Nitrate or sulfate.
3. the preparation method of a kind of mononuclear aromatics partial hydrogenation catalyst according to claim 2, it is characterised in that described
The halide of ruthenium is three hydrate ruthenium trichlorides, and the halide of the zinc is zinc chloride.
4. the preparation method of a kind of mononuclear aromatics partial hydrogenation catalyst according to claim 1, it is characterised in that in step
Suddenly in (2), the reaction vessel of the co-precipitation is beaker, flask or reactor.
5. the preparation method of a kind of mononuclear aromatics partial hydrogenation catalyst according to claim 1, it is characterised in that in step
Suddenly in (3), the time of the centrifugal sedimentation is 1-15min, and rotating speed is 750-3000rpm.
6. the preparation method of a kind of mononuclear aromatics partial hydrogenation catalyst according to claim 1, it is characterised in that in step
Suddenly in (4), the pressure of the pressurization is 1-7Mpa, and the temperature during high-speed stirred is 70-150 DEG C, speed 1000-
2000rpm, time 2-36h.
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| US20040077903A1 (en) * | 2001-01-31 | 2004-04-22 | Ken Suzuki | Process for producing cyclohexanone oxime |
| CN1533375A (en) * | 2001-07-25 | 2004-09-29 | ɻ�ѧ��ʽ���� | Process for producing cyclohexanone oxime |
| CN102264471A (en) * | 2008-12-22 | 2011-11-30 | 旭化成化学株式会社 | Method for producing ruthenium catalyst for producing cycloolefin, method for producing cycloolefin, and production device |
| CN103633311A (en) * | 2013-11-22 | 2014-03-12 | 武汉工程大学 | Preparation method of precursor of ternary cathode material for lithium ion battery |
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