CN105056943A - Production system of catalyst for preparation of cyclohexene by benzene selective hydrogenation and preparation method - Google Patents
Production system of catalyst for preparation of cyclohexene by benzene selective hydrogenation and preparation method Download PDFInfo
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 126
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 43
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000001556 precipitation Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000006722 reduction reaction Methods 0.000 claims abstract description 11
- 238000007599 discharging Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 112
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 53
- 230000032683 aging Effects 0.000 claims description 31
- 239000001257 hydrogen Substances 0.000 claims description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 26
- 239000003513 alkali Substances 0.000 claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 claims description 18
- 239000011343 solid material Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 7
- 241000370738 Chlorion Species 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000006073 displacement reaction Methods 0.000 claims description 6
- 229910000856 hastalloy Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 230000008676 import Effects 0.000 claims description 6
- 238000011017 operating method Methods 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- -1 polypropylene Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract 2
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 238000004904 shortening Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 9
- 239000000498 cooling water Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- YXIXIZVWHXLIMS-UHFFFAOYSA-N cyclohexanone;cyclohexene Chemical compound C1CCC=CC1.O=C1CCCCC1 YXIXIZVWHXLIMS-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Belonging to the field of chemical and chemical engineering, the invention in particular relates to a production system of a catalyst for preparation of cyclohexene by benzene selective hydrogenation and a method. The production system includes an elevated tank, a compounding tank, a high pressure kettle, a washing tank and the like. The preparation method comprises material compounding, precipitation reaction, reduction reaction and washing, etc. Compared with the prior art, in the catalyst preparation production system, the position difference between devices is utilized to realize automatic feeding and discharging, thus solving the high-pressure kettle mechanical seal oil leakage problem, shortening the catalyst preparation period from the original 24 hours to 8 hours, and increasing the catalyst production capacity from 1000kg/year to more than 3000kg/year; and in terms of the main performance indexes of the catalyst, when 70% of benzene converts, the cyclohexene selectivity reaches about 80%.
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of production system and method for producing cyclohexene with benzene selective hydrogenation catalyst.
Background technology
Take benzene as raw material selective hydrogenation to prepare cyclohexene, production safety, resources conservation, environmental friendliness.The bulk chemical such as Downstream Products from Cyclohexene cyclohexanone, adipic acid, nylon 6, nylon66 fiber have important function in the national economic development.But due to producing cyclohexene with benzene selective hydrogenation all totally unfavorable on thermodynamics and kinetics, generally, benzene hydrogenation can only obtain cyclohexane, only in some special catalysts and catalyst system and catalyzing, just can obtain cyclohexene.Although people have carried out extensive research to producing cyclohexene with benzene selective hydrogenation catalysis technique over nearly 40 years, Japan and China has been only had to achieve industrialization so far in the world.Preparation facilities and the technique of producing cyclohexene with benzene selective hydrogenation catalyst are then seldom reported.
Disclosed in present inventor seminar published " preparation method of the catalyst in producing cyclohexene with benzene selective hydrogenation and production equipment " patent (CN103785379A), preparation method is: precipitation reaction temperature controls at 50 ~ 60 DEG C, the stirring reaction time is 3 ~ 8h, then between 50 ~ 60 DEG C, still aging, the time is 6 ~ 12h; Reduction reaction temperature controls at 130 ~ 150 DEG C, reaction time 6 ~ 12h, obtains the catalyst feed liquid after reduction, then is 6.5 ~ 7.5 through washing to pH value, namely obtains target product.Utilize preparation method's Kaolinite Preparation of Catalyst disclosed in this patent, manufacturing cycle long (about 24h), production capacity is at about 1000 kgs/year, and in production equipment described in this patent, contain a vacuum system, its Main Function utilizes vacuum and atmospheric pressure to send in still by reaction mass, finds often to cause autoclave mechanical seal leakage of oil because vacuumizing in catalyst preparation process; In provided embodiment, catalyst the key technical indexes, when benzene transforms 60%, cyclohexene is selective reaches about 80%.
Summary of the invention
The object of the present invention is to provide production system and the method for another producing cyclohexene with benzene selective hydrogenation catalyst.
For achieving the above object, the technical scheme taked of the present invention is as follows:
A kind of production system of producing cyclohexene with benzene selective hydrogenation catalyst: this production system comprises from top to bottom spaced head tank successively, material-compound tank, autoclave, washing tank group, described washing tank group comprises at least one washing tank, the bottom of head tank respectively with material-compound tank, autoclave, the top of washing tank is connected, the top of autoclave is provided with blast pipe, and the top of autoclave is also connected with the bottom of material-compound tank while being connected with the bottom of head tank, the middle part of autoclave simultaneously and nitrogen pipeline, Hydrogen Line is connected, the bottom of autoclave is provided with discharge duct, the middle part of discharge duct is connected with the top of washing tank, the sidewall of washing tank is provided with at least one drainpipe, the bottom of washing tank is provided with discharge nozzle, agitator is equipped with in material-compound tank, autoclave, washing tank, aforementioned being connected all refers to be connected by pipeline, and these pipelines and discharge duct, blast pipe, discharge nozzle, drainpipe, nitrogen pipeline, Hydrogen Line are equipped with valve.
Preferably, material-compound tank is positioned at the oblique below of head tank, and autoclave is positioned at the oblique below of material-compound tank, and washing tank is positioned at the oblique below of autoclave.
Preferably, material-compound tank, autoclave, washing tank top and be connected to the bottom of head tank.
Preferably, described autoclave adopts self sucking high-pressure still and magnetic seal, ratio of height to diameter 2.0 ~ 2.2:1, liner polytetrafluoro or C276 Hastelloy.
Preferably, introduce the foreign ions such as Fe, Cr, Ni for avoiding ironware to cause damage to catalyst, pipeline all adopts polytetrafluoro or polypropylene plastics, discharge duct, blast pipe, discharge nozzle, drainpipe, nitrogen pipeline, Hydrogen Line all adopt C276 Hastelloy, and all valves all adopt polytetrafluoro or polypropylene plastics.
Preferably, for ensureing that in material, gas, solid, liquid three-phase fully contact, reduce resistance to mass tranfer, two-layer stirring vane is equipped with in the shaft bottom of the agitator in autoclave, ground floor is positioned at counts up 1/5 still eminence at the bottom of still, and the second layer is positioned at counts up 3/5 still eminence at the bottom of still.
Preferably, the sidewall of washing tank is provided with two drainpipes, to lay respectively at from bottom up 20-40cm place and 60-80cm place.
Utilize aforementioned production system to prepare a method for producing cyclohexene with benzene selective hydrogenation catalyst, operating procedure is as follows:
(1), batching: first added water in material-compound tank by head tank, then NaOH is added under stirring, be mixed with alkali lye, then alkali lye is imported autoclave from material-compound tank, open the agitator of autoclave simultaneously; Ruthenium trichloride hydrate is put into material-compound tank, is then added water in material-compound tank by head tank, stirring and dissolving, is mixed with saline solution, then imports in autoclave by saline solution;
(2), precipitation reaction: alkali lye and saline solution in autoclave in 20 ~ 60 DEG C, precipitation reaction 1 ~ 2h under speed of agitator 100 ~ 150r/min, then ageing 0.5 ~ 1h, carry out, with in ageing process, remaining that autoclave leads to air in precipitation reaction, the complete material pH value of ageing is more than 10;
(3), reduction reaction: autoclave is sealed, first by nitrogen pipeline air in nitrogen displacement autoclave, again by Hydrogen Line nitrogen in hydrogen exchange autoclave, 135 ~ 145 DEG C, 4.5 ~ 5.5MPa hydrogen pressure, reduction reaction 3 ~ 5h under 150 ~ 200r/min condition, then ageing 1 ~ 2h, ageing is complete, opens blast pipe and keeps autoclave to lead to air, finally open discharge duct and draw off solid material, supernatant material pH value is more than 10;
(4), washing: imported by the solid material of step (3) in washing tank, head tank adds water washing extremely without chlorion in washing tank, and cleaning solution pH value is 6.5 ~ 7.5, and namely the solid material after washing obtains target product after discharging opening is discharged.
Preferably, in step (1), during preparation alkali lye, the mass ratio of NaOH and water is 1:3 ~ 10; During preparation saline solution, the mass ratio of ruthenium trichloride hydrate and water is 1:8 ~ 15; Saline solution and alkali lye press ruthenium trichloride hydrate: the mol ratio 1:3 mixing of NaOH.
Compared with prior art, the invention has the advantages that:
1, in Catalyst Production system, utilizing the potential difference automatic feed between device and discharge, solving the autoclave mechanical seal Leakage caused because vacuumizing in catalyst preparation process.
2, shorten the catalyst preparing cycle, shorten to about 8h by original about 24h, catalyst productivity also brings up to more than 3000 kgs/year by 1000 kgs/year.
3, catalyst main performance index, to bring up to when benzene transforms 70% that cyclohexene is selective reaches about 80%.
Accompanying drawing explanation
Fig. 1: the structural representation of production system of the present invention; Wherein 1-head tank, 2-material-compound tank, 3-autoclave, 4-washing tank, 5-blast pipe, 6-nitrogen pipeline, 7-Hydrogen Line, 8-discharge duct, 9-drainpipe, 10-agitator, 11-discharge nozzle;
Fig. 2: the process chart of preparation method of the present invention.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described, but do not limit protection scope of the present invention.
Embodiment 1
As shown in Figure 1, a kind of production system of producing cyclohexene with benzene selective hydrogenation catalyst: this production system comprises from top to bottom spaced head tank 1 successively, material-compound tank 2, autoclave 3, washing tank group, described washing tank group comprises two washing tanks 4, material-compound tank 2 is positioned at the left tiltedly below of head tank 1, autoclave 3 is positioned at the left tiltedly below of material-compound tank 2, washing tank 4 is positioned at the right tiltedly below of autoclave 3, the bottom of head tank 1 respectively with material-compound tank 2, autoclave 3, connected (the material-compound tank 2 in top of washing tank 4, autoclave 3, the top of washing tank 4 is also connected to the bottom of head tank 1), the top of autoclave 3 is provided with blast pipe 5, and the top of autoclave 3 is also connected with the bottom of material-compound tank 2 while being connected with the bottom of head tank 1, the middle part of autoclave 3 simultaneously with nitrogen pipeline 6, Hydrogen Line 7 is connected, the bottom of autoclave 3 is provided with discharge duct 8, the middle part of discharge duct 8 is connected with the top of washing tank 4, the sidewall of washing tank 4 is provided with two drainpipes 9, to lay respectively at from bottom up 30cm place and 80cm place, the bottom of washing tank 4 is provided with discharge nozzle 11, be equipped with agitator 10 in material-compound tank 2, autoclave 3, washing tank 4, two-layer stirring vane is equipped with in the shaft bottom of the agitator 10 in autoclave 3, and ground floor is positioned at counts up 1/5 still eminence at the bottom of still, and the second layer is positioned at counts up 3/5 still eminence at the bottom of still, aforementioned being connected all refers to be connected by pipeline, and these pipelines (all adopting poly fourfluoroplastics) and discharge duct 8, blast pipe 5, discharge nozzle 11, drainpipe 9, nitrogen pipeline 6, Hydrogen Line 7(all adopt C276 Hastelloy) on be equipped with valve (all adopting poly fourfluoroplastics), wherein, described autoclave 3 adopts self sucking high-pressure still and magnetic seal, ratio of height to diameter 2.0:1, liner polytetrafluoro.
Utilize above-mentioned production system to prepare the method for producing cyclohexene with benzene selective hydrogenation catalyst, operating procedure is as follows:
(1), prepare burden: first added water in material-compound tank 2 by head tank 1, then NaOH is added under stirring, be mixed with alkali lye, the mass ratio of NaOH and water is 1:3, again alkali lye is imported autoclave 3 from material-compound tank 2, open the agitator 10 of autoclave 3, rotating speed 100r/min simultaneously; Ruthenium trichloride hydrate is put into material-compound tank 2, then added water in material-compound tank 2 by head tank 1, stirring and dissolving, is mixed with saline solution, and the mass ratio of ruthenium trichloride hydrate and water is 1:8; Again saline solution is imported in autoclave 3; Saline solution and the alkali lye mixed proportion in autoclave 3 ensures ruthenium trichloride hydrate: the mol ratio of NaOH is 1:3;
(2), precipitation reaction: alkali lye and saline solution in 30 DEG C, precipitation reaction 1h, then ageing 0.5h under speed of agitator 100r/min, carry out with in ageing process in precipitation reaction, remain that autoclave 3 leads to air, the complete material pH value 10 of ageing in autoclave 3;
(3), reduction reaction: autoclave 3 is sealed, first by nitrogen pipeline 6 air 3 times in nitrogen displacement autoclave 3, then by Hydrogen Line 7 nitrogen in hydrogen exchange autoclave 33 times, imports hydrogen to 4.5MPa; Confirm each valve state, confirm without revealing, then agitator 10 is opened, rotating speed controls at 100r/min, starts to heat up, heating rate 1.5 DEG C/min, rise to 135 DEG C and start timing, and speed of agitator is increased to 150r/min simultaneously, 135 DEG C, 4.5MPa hydrogen pressure, react 3h, then ageing 1h under speed of agitator 150r/min condition; Ageing is complete, opens blast pipe 5 and keeps autoclave 3 to lead to air, and pass into cooling water temperature, be down to 50 DEG C, open discharge duct 8 and draw off solid material, supernatant material pH value 10;
(4), washing: imported by the solid material of step (3) in washing tank 4, head tank 1 adds water washing extremely without chlorion in washing tank 4, and cleaning solution pH value is 6.5, and the solid material after washing is drying to obtain finished catalyst after discharge nozzle 11 is discharged.
Catalyst the key technical indexes detects:
Catalyst the key technical indexes comprises the selective and yield of catalyst activity, cyclohexene, and overall target activity index represents.Benzene selective hydrogenation reaction is carried out in GS-1 type Hastelloy still: add the catalyst that 1.96g embodiment 1 prepares, 49.2gZnSO
47H
2o, 280mlH
2o, at H
2pressure is 5.0MPa and stir speed (S.S.) is under the condition of 800r/min, adds 140ml benzene after being warming up to 150 DEG C, and adjusting rotary speed, to 1400r/min, starts timing, samples every 5min.Adopt chromatographic product composition, fid detector, area corrects the relative amount of normalization method ring hexane, cyclohexene and benzene, calculates not the conversion ratio C of benzene in the same time
bZ, cyclohexene selective S
hEwith yield Y
hE.Benzene conversion ratio C
bZ, the selective S of cyclohexene
hEwith yield Y
hEand activity index γ computing formula is as follows:
In (4) formula, V
bZ(140) the volume 140ml of benzene is referred to, ρ
bZ(0.88) density 0.88, C of benzene is referred to
bZ(0.4) refer to that the conversion ratio of benzene is 40%, t
40h () refers to the time transforming 40% with the benzene hour to represent, W
cat(1.96) the quality 1.96g of catalyst is referred to, activity index γ
40the grams of every gram of catalyst conversion benzene per hour when representing that benzene transforms 40%, the rest may be inferred γ
50, γ
60, γ
70then represent the grams of every gram of catalyst conversion benzene per hour during benzene conversion 50%, 60%, 70% respectively, as calculating γ
50, γ
60, γ
70time, respectively by C
bZ(0.4) C is changed into
bZ(0.5), C
bZand C (0.6)
bZ(0.7), t
40h () changes t into
50(h), t
60(h) and t
70(h).The Activity evaluation of embodiment 1 gained catalyst is as shown in table 1.
Embodiment 1 gained catalyst the key technical indexes is as follows:
t
40=12min，γ
40=126，S
40=84%；
t
50=15min，γ
50=126，S
50=83%；
t
60=18min，γ
60=126，S
60=80%；
t
70=18min，γ
70=126，S
70=77%；
Wherein, t
40, t
50, t
60, t
70be respectively the time that benzene transforms 40%, 50%, 60%, 70%; γ
40, γ
50, γ
60, γ
70be respectively the activity index that benzene transforms 40%, 50%, 60%, 70%; S
40, S
50, S
60, S
70the cyclohexene being respectively benzene conversion 40%, 50%, 60%, 70% correspondence is selective.
Embodiment 2
A kind of production system of producing cyclohexene with benzene selective hydrogenation catalyst is with embodiment 1.
Utilize above-mentioned production system to prepare the method for producing cyclohexene with benzene selective hydrogenation catalyst, operating procedure is as follows:
(1), prepare burden: first added water in material-compound tank 2 by head tank 1, then NaOH is added under stirring, be mixed with alkali lye, the mass ratio of NaOH and water is 1:5, again alkali lye is imported autoclave 3 from material-compound tank 2, open the agitator 10 of autoclave 3, rotating speed 120r/min simultaneously; Ruthenium trichloride hydrate is put into material-compound tank 2, then added water in material-compound tank 2 by head tank 1, stirring and dissolving, is mixed with saline solution, and the mass ratio of ruthenium trichloride hydrate and water is 1:10; Imported by saline solution in autoclave 3, saline solution and the alkali lye mixed proportion in autoclave 3 ensures ruthenium trichloride hydrate: the mol ratio of NaOH is 1:3 again;
(2), precipitation reaction: alkali lye and saline solution in autoclave 3 in 30 DEG C, precipitation reaction 1.2h under speed of agitator 120r/min, then ageing 0.6h, carry out with in ageing process in precipitation reaction, remain that autoclave 3 leads to air, the complete material pH value 12 of ageing;
(3), reduction reaction: autoclave 3 is sealed, first by nitrogen pipeline 6 air 3 times in nitrogen displacement autoclave 3, then by Hydrogen Line 7 nitrogen in hydrogen exchange autoclave 33 times, imports hydrogen to 4.8MPa; Confirm each valve state, confirm without revealing, then agitator 10 is opened, rotating speed controls at 120r/min, starts to heat up, heating rate 1.5 DEG C/min, rise to 140 DEG C and start timing, and speed of agitator is increased to 160r/min simultaneously, 140 DEG C, 4.8MPa hydrogen pressure, react 3.5h, then ageing 1.5h under speed of agitator 160r/min condition; Ageing is complete, opens blast pipe 5 and keeps autoclave 3 to lead to air, and pass into cooling water temperature, be down to 50 DEG C, open discharge duct 8 and draw off solid material, supernatant material pH value 12;
(4), washing: imported by the solid material of step (3) in washing tank 4, head tank 1 adds water washing extremely without chlorion in washing tank 4, and cleaning solution pH value is 6.8, and the solid material after washing is drying to obtain finished catalyst after discharge nozzle 11 is discharged.
Catalyst the key technical indexes detection method is with embodiment 1, and the Activity evaluation of embodiment 2 gained catalyst is as shown in table 2.
Embodiment 2 gained catalyst the key technical indexes is as follows:
t
40=12min，γ
40=126，S
40=88%；
t
50=14min，γ
50=135，S
50=86%；
t
60=18min，γ
60=126，S
60=83%；
t
70=22min，γ
70=120，S
70=80%。
Embodiment 3
A kind of production system of producing cyclohexene with benzene selective hydrogenation catalyst is with embodiment 1.
Utilize above-mentioned production system to prepare the method for producing cyclohexene with benzene selective hydrogenation catalyst, operating procedure is as follows:
(1), prepare burden: first added water in material-compound tank 2 by head tank 1, then NaOH is added under stirring, be mixed with alkali lye, the mass ratio of NaOH and water is 1:7, again alkali lye is imported autoclave 3 from material-compound tank 2, open the agitator 10 of autoclave 3, rotating speed 135r/min simultaneously; Ruthenium trichloride hydrate is put into material-compound tank 2, then added water in material-compound tank 2 by head tank 1, stirring and dissolving, is mixed with saline solution, and the mass ratio of ruthenium trichloride hydrate and water is 1:12; Imported by saline solution in autoclave 3, saline solution and the alkali lye mixed proportion in autoclave 3 ensures ruthenium trichloride hydrate: the mol ratio of NaOH is 1:3 again;
(2), precipitation reaction: alkali lye and saline solution in autoclave 3 in 30 DEG C, precipitation reaction 1.8h under speed of agitator 120r/min, then ageing 0.8h, carry out with in ageing process in precipitation reaction, remain that autoclave 3 leads to air, the complete material pH value 13 of ageing;
(3), reduction reaction: autoclave 3 is sealed, first by nitrogen pipeline 6 air 3 times in nitrogen displacement autoclave 3, then by Hydrogen Line 7 nitrogen in hydrogen exchange autoclave 33 times, imports hydrogen to 5.2MPa; Confirm each valve state, confirm without revealing, then agitator 10 is opened, rotating speed controls at 140r/min, starts to heat up, heating rate 1.5 DEG C/min, rise to 145 DEG C and start timing, and speed of agitator is increased to 180r/min simultaneously, 145 DEG C, 5.2MPa hydrogen pressure, react 4h, then ageing 1.8h under speed of agitator 180r/min condition; Ageing is complete, opens blast pipe 5 and keeps autoclave 3 to lead to air, and pass into cooling water temperature, be down to 50 DEG C, open discharge duct 8 and draw off solid material, supernatant material pH value 13;
(4), washing: imported by the solid material of step (3) in washing tank 4, head tank 1 adds water washing extremely without chlorion in washing tank 4, and cleaning solution pH value is 7.0, and the solid material after washing is drying to obtain finished catalyst after discharge nozzle 11 is discharged.
Catalyst the key technical indexes detection method is with embodiment 1, and the Activity evaluation of embodiment 3 gained catalyst is as shown in table 3.
Embodiment 3 gained catalyst the key technical indexes is as follows:
t
40=14min，γ
40=108，S
40=86%；
t
50=17min，γ
50=111，S
50=85%；
t
60=20min，γ
60=113，S
60=83%；
t
70=24min，γ
70=110，S
70=80%。
Embodiment 4
A kind of production system of producing cyclohexene with benzene selective hydrogenation catalyst is with embodiment 1.
Utilize above-mentioned production system to prepare the method for producing cyclohexene with benzene selective hydrogenation catalyst, operating procedure is as follows:
(1), prepare burden: first added water in material-compound tank 2 by head tank 1, then NaOH is added under stirring, be mixed with alkali lye, the mass ratio of NaOH and water is 1:10, again alkali lye is imported autoclave 3 from material-compound tank 2, open the agitator 10 of autoclave 3, rotating speed 150r/min simultaneously; Ruthenium trichloride hydrate is put into material-compound tank 2, then added water in material-compound tank 2 by head tank 1, stirring and dissolving, is mixed with saline solution, and the mass ratio of ruthenium trichloride hydrate and water is 1:15; Imported by saline solution in autoclave 3, saline solution and the alkali lye mixed proportion in autoclave 3 ensures ruthenium trichloride hydrate: the mol ratio of NaOH is 1:3 again;
(2), precipitation reaction: alkali lye and saline solution in 30 DEG C, precipitation reaction 2h, then ageing 1h under speed of agitator 150r/min, carry out with in ageing process in precipitation reaction, remain that autoclave 3 leads to air, the complete material pH value 14 of ageing in autoclave 3;
(3), reduction reaction: autoclave 3 is sealed, first by nitrogen pipeline 6 air 3 times in nitrogen displacement autoclave 3, then by Hydrogen Line 7 nitrogen in hydrogen exchange autoclave 33 times, imports hydrogen to 5.5MPa; Confirm each valve state, confirm without revealing, then agitator 10 is opened, rotating speed controls at 140r/min, starts to heat up, heating rate 1.5 DEG C/min, rise to 150 DEG C and start timing, and speed of agitator is increased to 200r/min simultaneously, 150 DEG C, 5.5MPa hydrogen pressure, react 5h, then ageing 2h under speed of agitator 200r/min condition; Ageing is complete, opens blast pipe 5 and keeps autoclave 3 to lead to air, and pass into cooling water temperature, be down to 60 DEG C, open discharge duct 8 and draw off solid material, supernatant material pH value 14;
(4), washing: imported by the solid material of step (3) in washing tank 4, head tank 1 adds water washing extremely without chlorion in washing tank 4, and cleaning solution pH value is 7.5, and the solid material after washing is drying to obtain finished catalyst after discharge nozzle 11 is discharged.
Catalyst the key technical indexes detection method is with embodiment 1, and the Activity evaluation of embodiment 4 gained catalyst is as shown in table 4.
Embodiment 4 gained catalyst the key technical indexes is as follows:
t
40=15min，γ
40=101，S
40=87%；
t
50=18min，γ
50=105，S
50=85%；
t
60=24min，γ
60=94，S
60=83%；
t
70=31min，γ
70=85，S
70=79%。
Above preferred embodiment of the present invention has been described in detail, but described content being only preferred embodiment of the present invention, can not being considered to for limiting practical range of the present invention.All equalizations done according to the present patent application scope change and improve, and all should still belong within patent covering scope of the present invention.
Claims (9)
1. the production system of a producing cyclohexene with benzene selective hydrogenation catalyst, it is characterized in that: this production system comprises from top to bottom spaced head tank successively, material-compound tank, autoclave, washing tank group, described washing tank group comprises at least one washing tank, the bottom of head tank respectively with material-compound tank, autoclave, the top of washing tank is connected, the top of autoclave is provided with blast pipe, and the top of autoclave is also connected with the bottom of material-compound tank while being connected with the bottom of head tank, the middle part of autoclave simultaneously and nitrogen pipeline, Hydrogen Line is connected, the bottom of autoclave is provided with discharge duct, the middle part of discharge duct is connected with the top of washing tank, the sidewall of washing tank is provided with at least one drainpipe, the bottom of washing tank is provided with discharge nozzle, agitator is equipped with in material-compound tank, autoclave, washing tank, aforementioned being connected all refers to be connected by pipeline, and these pipelines and discharge duct, blast pipe, discharge nozzle, drainpipe, nitrogen pipeline, Hydrogen Line are equipped with valve.
2. production system as claimed in claim 1, it is characterized in that: material-compound tank is positioned at the oblique below of head tank, autoclave is positioned at the oblique below of material-compound tank, and washing tank is positioned at the oblique below of autoclave.
3. production system as claimed in claim 1, is characterized in that: the top of material-compound tank, autoclave, washing tank is also connected to the bottom of head tank.
4. production system as claimed in claim 1, is characterized in that: described autoclave adopts self sucking high-pressure still and magnetic seal, ratio of height to diameter 2.0 ~ 2.2:1, liner polytetrafluoro or C276 Hastelloy.
5. production system as claimed in claim 1, it is characterized in that: pipeline all adopts polytetrafluoro or polypropylene plastics, discharge duct, blast pipe, discharge nozzle, drainpipe, nitrogen pipeline, Hydrogen Line all adopt C276 Hastelloy, and all valves all adopt polytetrafluoro or polypropylene plastics.
6. production system as claimed in claim 1, it is characterized in that: two-layer stirring vane is equipped with in the shaft bottom of the agitator in autoclave, ground floor is positioned at counts up 1/5 still eminence at the bottom of still, and the second layer is positioned at counts up 3/5 still eminence at the bottom of still.
7. production system as claimed in claim 1, is characterized in that: the sidewall of washing tank is provided with two drainpipes, to lay respectively at from bottom up 20-40cm place and 60-80cm place.
8. utilize the arbitrary described production system of claim 1-7 to prepare a method for producing cyclohexene with benzene selective hydrogenation catalyst, it is characterized in that operating procedure is as follows:
(1), batching: first added water in material-compound tank by head tank, then NaOH is added under stirring, be mixed with alkali lye, then alkali lye is imported autoclave from material-compound tank, open the agitator of autoclave simultaneously; Ruthenium trichloride hydrate is put into material-compound tank, is then added water in material-compound tank by head tank, stirring and dissolving, is mixed with saline solution, then imports in autoclave by saline solution;
(2), precipitation reaction: alkali lye and saline solution in autoclave in 20 ~ 60 DEG C, precipitation reaction 1 ~ 2h under speed of agitator 100 ~ 150r/min, then ageing 0.5 ~ 1h, carry out, with in ageing process, remaining that autoclave leads to air in precipitation reaction, the complete material pH value of ageing is more than 10;
(3), reduction reaction: autoclave is sealed, first by nitrogen pipeline air in nitrogen displacement autoclave, again by Hydrogen Line nitrogen in hydrogen exchange autoclave, 135 ~ 145 DEG C, 4.5 ~ 5.5MPa hydrogen pressure, reduction reaction 3 ~ 5h under 150 ~ 200r/min condition, then ageing 1 ~ 2h, ageing is complete, opens blast pipe and keeps autoclave to lead to air, finally open discharge duct and draw off solid material, supernatant material pH value is more than 10;
(4), washing: imported by the solid material of step (3) in washing tank, head tank adds water washing to being 6.5 ~ 7.5 without chlorion, cleaning solution pH value in washing tank, and namely the solid material after washing obtains target product after discharging opening is discharged.
9. preparation method as claimed in claim 8, is characterized in that in step (1), and during preparation alkali lye, the mass ratio of NaOH and water is 1:3 ~ 10; During preparation saline solution, the mass ratio of ruthenium trichloride hydrate and water is 1:8 ~ 15; Saline solution and alkali lye press ruthenium trichloride hydrate: the mol ratio 1:3 mixing of NaOH.
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| CN114618488A (en) * | 2022-05-12 | 2022-06-14 | 北京润景未来新材料科技有限公司 | Preparation method of cyclohexene bimetal alloy microcrystalline catalyst by hydrogenation |
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| CN2378111Y (en) * | 1999-05-27 | 2000-05-17 | 王辑五 | Continuous photochemical reactor |
| CN203183974U (en) * | 2012-10-30 | 2013-09-11 | 刘方旭 | Strong-magnetic sealed high-pressure reaction kettle |
| CN103785379A (en) * | 2014-03-04 | 2014-05-14 | 河北石焦化工有限公司 | Preparation method and production device of catalyst for cyclohexene preparation through benzene selective hydrogenation |
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|---|---|---|---|---|
| US3558736A (en) * | 1966-08-26 | 1971-01-26 | Sentralinst For Ind Forskning | Process for the production of 3-methyl pentenes from ethene |
| CN2378111Y (en) * | 1999-05-27 | 2000-05-17 | 王辑五 | Continuous photochemical reactor |
| CN203183974U (en) * | 2012-10-30 | 2013-09-11 | 刘方旭 | Strong-magnetic sealed high-pressure reaction kettle |
| CN103785379A (en) * | 2014-03-04 | 2014-05-14 | 河北石焦化工有限公司 | Preparation method and production device of catalyst for cyclohexene preparation through benzene selective hydrogenation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114618488A (en) * | 2022-05-12 | 2022-06-14 | 北京润景未来新材料科技有限公司 | Preparation method of cyclohexene bimetal alloy microcrystalline catalyst by hydrogenation |
| CN114618488B (en) * | 2022-05-12 | 2023-01-31 | 北京润景未来新材料科技有限公司 | Preparation method of cyclohexene bimetal alloy microcrystalline catalyst by hydrogenation |
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