CN1817917A - Method and apparatus for preparing microsphere silicon dioxide carrier on gas-phase fluidized bed by polyvinyls catalyst - Google Patents
Method and apparatus for preparing microsphere silicon dioxide carrier on gas-phase fluidized bed by polyvinyls catalyst Download PDFInfo
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- CN1817917A CN1817917A CN 200610016568 CN200610016568A CN1817917A CN 1817917 A CN1817917 A CN 1817917A CN 200610016568 CN200610016568 CN 200610016568 CN 200610016568 A CN200610016568 A CN 200610016568A CN 1817917 A CN1817917 A CN 1817917A
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- dioxide
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 21
- 235000012239 silicon dioxide Nutrition 0.000 title claims description 40
- 239000003054 catalyst Substances 0.000 title claims description 22
- 239000004005 microsphere Substances 0.000 title claims description 11
- 229920002554 vinyl polymer Polymers 0.000 title abstract description 9
- 238000009826 distribution Methods 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 10
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 229960001866 silicon dioxide Drugs 0.000 claims description 44
- 238000002360 preparation method Methods 0.000 claims description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- 238000004945 emulsification Methods 0.000 claims description 7
- 238000013467 fragmentation Methods 0.000 claims description 7
- 238000006062 fragmentation reaction Methods 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 239000003607 modifier Substances 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 5
- 239000000084 colloidal system Substances 0.000 abstract description 4
- 239000002685 polymerization catalyst Substances 0.000 abstract description 4
- 239000007921 spray Substances 0.000 abstract description 4
- 239000012467 final product Substances 0.000 abstract 1
- 238000012856 packing Methods 0.000 abstract 1
- 238000001694 spray drying Methods 0.000 abstract 1
- 239000002002 slurry Substances 0.000 description 14
- 239000000499 gel Substances 0.000 description 12
- 239000010419 fine particle Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 229920001903 high density polyethylene Polymers 0.000 description 5
- 239000004700 high-density polyethylene Substances 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 241001269238 Data Species 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 235000010210 aluminium Nutrition 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- 230000011218 segmentation Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000001033 granulometry Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- Catalysts (AREA)
Abstract
Production and apparatus for microspheroidal silica carrier of gas-phase fluidized bed vinyl polymerization catalyst are disclosed. The process is carried out by adding modified sol into colloid mill, adding urea to treat, 3~20mins later, spray drying atomized disk on top, mixing with 300~400DEG C hot air from tangent inlet on top of spray drier, high-speed rotating downward, and putting it with microspheroidal silica from outlet on bottom of one-stage cyclone separator and spray drier into calciner for 1.5-2.0hrs to obtain final product. The granularity distribution is d50 30.15~48.59um, d10 9.23~214.97um, d9052.37~75.59um, packing density is 0.29~0.32g/ml, specific area is 297.2~310.2m2/g,pore volume is 1.57~1.64ml/g and average aperture is 200+-20.
Description
Technical field
The present invention relates to the preparation method and the equipment of vinyl polymerization, ethene and alhpa olefin catalyst for copolymerization carrier, relate in particular to the preparation method and the equipment of microsphere silicon dioxide carrier on gas-phase fluidized bed by polyvinyls catalyst.
Background technology
Ethene is the main representative products of petrochemical complex.The production of vinyl group product and application are the important yardsticks of weighing a countries and regions petrochemical complex developmental level.Polyethylene is the most important derivative in ethene downstream, accounts for 70% of world Ethylene total amount.
With the catalyzer that microspheroidal silicon-dioxide is made as carrier, be widely used in fluidized-bed reaction production of linear new LDPE (film grade) (LLDPE), fluidized-bed reaction production high density polyethylene(HDPE) (HDPE), both output account for 30% of world's polyethylene ultimate production.
Catalyzer for gas-phase fluidized bed production LLDPE and HDPE should satisfy the kinetics of polymerization reaction requirement, and suitable specific surface area, pore volume and suitable aperture and pore size distribution should be arranged; Also will satisfy the requirement on the polymerization engineering, suitable tap density should be arranged, suitable particle diameter and size distribution have good flowability and suitable physical strength again.Jiangsu is permitted people such as high honour and is disclosed in the CN93236555.8 patent specification by a kind of air-flow effect, make material in the volute chamber by shunting, volute chamber and secondary chamber separate coarse fodder and fines by classification.Yet be difficult to reach needed size-grade distribution.
U.S. Cabot Corporation and Chinese CN1116845 and WO94,16995, a kind of air-flowing type plastochondria size classification machine is proposed, with particle diameter less than the isolating method of the silicon-dioxide of 45 μ m, by means of the bump utmost point (plate) that predetermined angular is installed, be evenly distributed in the container fine particle rising after making air-flow and suspended substance bump in special container, macrobead is deposited on the bottom, is able to coarse grain and particulate are separated.This coarse grain bump breaking method owing to form unformed powder, obviously is unsuitable for the manufacturing of the little shape of ball.
Japanese Patent JP2004160305 HAGINO TAKAO proposes to isolate the solid particulate in the suspension with band shower nozzle cylindrical vessel, and this fractionated method does not reach the granulometry that we set.
For satisfying the requirement of polymerization reaction engineering, the given standard of microspheroidal silicon-dioxide of the SylopolRTM955 trade mark of U.S. Grace company, its particle diameter and size distribution d
5035～49 μ m, d
90≯ 97 μ m, d
10≯ 10 μ m can satisfy the requirement of carrier for olefin polymerization catalyst preferably, and oneself is widely used on the suitability for industrialized production.But in GB12116638 patent and later patent, concrete gradation method is not proposed all.
More than saidly satisfy gas-phase fluidized-bed reaction engineering requirement, be meant that the microspheroidal Titanium series catalyst makes ethene and alhpa olefin coordination copolymerization in fluidized-bed, produce LLDPE, or the microspheroidal chromium-based catalysts is at gas-phase fluidized-bed ethylene homo or ethene and propylene or butylene hydrocarbon copolymerization production HDPE.The specific area of this micro-spherical catalyst, pore volume, tap density, particle diameter, intensity are applicable in the fluidized-bed and operate.And the formation of these key elements is the carriers (being the character of microspheroidal silicon-dioxide) that depend on the load of various active ingredient institute.The Sylopol RTM955 silica gel of U.S. Grace company is the silica gel that generally adopts in the world.The gas-phase fluidized bed polyethylene industry of China also all adopts this carrier.With the catalyzer that this carrier is made, satisfied the engine request of gas-phase fluidized-bed reaction preferably.
Above mentioned Sylopol RTM955 silica gel (microspheroidal silicon-dioxide) correlation technique index is: tap density 0.25～0.37g/ml, specific surface area 289～355m2/g, size distribution d
5035～49 μ m, d
90≯ 97 μ m, d
10≮ 10 μ m.
The Beijing Tsinghua Luyin Technology Development Co.ltd is with the patent of Jilin Jiqing Science ﹠ Technology Development Co., Ltd co-applications, its application number 200410039492.1 " as the preparation method of the microspheroidal titanium dioxide silicon of carrier for olefin polymerization catalyst ", the method with " gel-sol-gel " of having announced prepares the microspheroidal silica supports, comprises the steps: 1) SiO in the initial gel is provided
2Weight content is 20～50%; 2) the initial gel of refinement makes it become SiO
2Median size is 10～100nm SiO
2Colloidal sol adds modifier A, B, C successively in the homogeneous micronization, wherein A is organic or inorganic acid, and making its pH is 0.5～4; B is for comprising the composition of the tensio-active agent of a kind of positively charged ion, negatively charged ion or nonionogenic tenside at least, and its consumption is every mole of SiO
23.42 * 10
-5～3.42 * 10
-4Mole; Properties-correcting agent C is selected from urea, methane amide or oxalic acid, or its composition, and its consumption is every mole of SiO
20.085～0.85 mole; 3) to resultant SiO
2Colloidal sol carries out spraying drying, and 300～370 ℃ of this dryer inlet temperatures, 100～200 ℃ of temperature outs, spraying disc rotating speed are 8000～30000rpm, obtain SiO
2The gel particle diameter is at the microspheroidal SiO of 10～70 μ m
2Gel; 4) to 3) the microspheroidal SiO that obtains
2Gel carries out roasting in stoving oven, obtain microspheroidal SiO
2More than be the present invention and the total necessary constructed feature of prior art.But, the prior art of application number 200410039492.1 " as the preparation method of the microspheroidal titanium dioxide silicon of carrier for olefin polymerization catalyst ", gel also need be handled 15-45 minute in 3000～10000rpm shears after the refinement in colloidal mill, roasting that the microspheroidal titanium dioxide silicon gel of gained needs to divide three sections in stoving oven to carry out (keeping 1-2 hour, 200～400 ℃ according to 100～200 ℃ keeps 0.5-1.5 hour, 550～750 ℃ programs that kept 3-5 hour to carry out roasting), required roasting time is long, and power consumption is high; This shows the prior art long flow path.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, a kind of preparation method and equipment of microsphere silicon dioxide carrier on gas-phase fluidized bed by polyvinyls catalyst are provided, colloidal sol after the modification is added in the colloidal mill, after adding the further modification processing of urea again, do not need to handle with shears again, simplify flow process; Under 600 ℃, do not need the segmentation roasting, to cut down the consumption of energy.
The objective of the invention is to realize by following technical scheme:
The preparation method of microsphere silicon dioxide carrier on gas-phase fluidized bed by polyvinyls catalyst will be with organic acid or mineral acid properties-correcting agent, and with cationic, anionic or nonionic surface active agent composition modified dose carries out modification to colloidal sol; Colloidal sol after the modification adds in the colloidal mill, wherein the silica solid weight percent is divided content 5～25%, adding its weight simultaneously is the properties-correcting agent urea of colloidal sol weight 0.1～2%, fragmentation through 3～20 minutes, after refinement and the emulsification, the centrifugal spraying dish of 10～12 curved cylinders that are provided with through spray cone moisture eliminator top, linear velocity with 45.8 meter per seconds～91.63 meter per seconds, with the hot blast that from the temperature of its below (atomizing disk below) is 300～400 ℃ in the tangent line ingress of spray-dryer upper lateral part, spirally in the same way rapidly be rotated down motion, spray-dried device bottom cone one side outlet enters primary cyclone, the microspheroidal silicon-dioxide that bottom this cyclonic separator, comes out, the microspheroidal silicon-dioxide that comes out with the spray-dryer bottom enters and carries out roasting in the stoving oven, make microspheroidal silicon-dioxide, its key technical indexes is: size-grade distribution d
5030.15～48.59 μ m, d
109.23～21.97 μ m, d
9052.37～75.59 μ m; Its tap density 0.29～0.32g/ml, its specific surface area 297.2～310.2m
2/ g, pore volume 1.57～1.64ml/g, average pore volume 200 ± 20 dusts.
Above-mentioned method, the linear velocity of its described hot blast are 10～20 meter per seconds.
Above-mentioned method, its described microspheroidal silicon-dioxide in stoving oven in 600 ℃ of following roastings 2 hours.
Realize the needed spray-dryer of preparation method of above-described microsphere silicon dioxide carrier on gas-phase fluidized bed by polyvinyls catalyst, the atomizing disk that it is characterized in that this spray-dryer top, its periphery is provided with 10～18 curved cylinders, is provided with the slit for the colloidal sol ejection between each curved cylinder.
Above-mentioned spray-dryer, its upper lateral part are positioned at the atomizing disk below and are provided with the tangent line inlet that hot wind supply enters.
With above-mentioned spray-dryer, be provided with primary cyclone in its cone one side; This cyclonic separator (6) links to each other with described spray-dryer cone by pipeline, and its lower end outlet links to each other with spray-dryer (4) lower end outlet pipe with pipeline.
The present invention compared with prior art has following marked improvement and positively effect:
The microspheroidal silicon dioxide gel that the gas-phase fluidized-bed ethylene rolymerization catalyst of the present invention is used, in " gel-sol-gel " preparation, only refinement in colloidal mill need not handled in high-speed shearing machine; During to the roasting of resulting silica dioxide gel, need not carry out roasting respectively at segmentation under the differing temps, only in stoving oven in 600 ℃ of roastings, flow process is short, energy consumption is low; Used spray-dryer top is provided with atomizing disk, and this atomizing disk periphery is provided with 10～18 curved cylinders; Hot blast enters moisture eliminator in the tangent line inlet that described moisture eliminator upper lateral part is positioned at the atomizing disk below, after colloidal sol enters atomizing disk, ejection back in slit moves downward with hot blast is spiral in the same way between curved cylinder from atomizing disk, prolongation is the residence time in moisture eliminator, after thinner microballoon silicon-dioxide enters primary cyclone, water vapor is discharged from described cyclonic separator top, trickleer preparing spherical SiO 2 enters stoving oven with the big microspheroidal silicon-dioxide of moisture eliminator bottom, reduce wherein water-content, the energy consumption in the time that roasting can being reduced; Therefore technical process of the present invention short.The size-grade distribution d that makes with this technical scheme
5030.15～48.59 μ m, d
109.23～21.97 μ m, d
9052.37～75.59 μ m; Tap density 0.29～0.32g/ml, specific surface area 297.2～310.2m
2/ g, pore volume 1.57～1.64ml/g, the microspheroidal silica supports of mean pore size 200 ± 20 dusts.This carrier can satisfy the requirement of preparation of industrialization polyolefin catalyst, can satisfy the requirement of the engineering of operating under the gas-phase fluidized-bed olefinic polymerization frozen state simultaneously again.With technical scheme of the present invention make on the microspheroidal silica supports, the titanium of producing is a series catalysts, uses on 300,000 tons of LLDPE full scale plants of the subordinate of China National Petroleum Corp., its processing parameter is:
Reaction pressure 2.15MPaG
87.5 ℃ of temperature of reaction
Vinyl group dividing potential drop 0.65～0.75MPaG
Triethyl aluminum concentration 350ppm
Static-0.01KV
During ethylene feed 30T/
Hydrogen add-on 5.5Kg/
During butylene add-on 2.48t/
The application manipulate is steady, can satisfy the ordinary production needs with the catalyzer of above-mentioned microspheroidal silica supports production, the catalyzer that alternative import silica-gel carrier is produced; Catalyzer with the production of above-mentioned microspheroidal silica supports is operated good fluidity under condensing state, no plugging phenomenon takes place; Show the catalyzer of producing with the microspheroidal silica supports of method production of the present invention through application testing, its activity is about 4000～4500KgPE/Kg catalyzer (originally used activity of such catalysts 3800～4500KgPE/Kg), tap density 365Kg/m
2(originally used catalyst buildup density 320～340Kg/m
2) about; During the application, above-mentioned catalyzer and butene-1 responsiveness are normal; The LLDPE powder product performance test shows that obtains has reached the national product quality standard with the PFDA-7042 trade mark linear low density polyethylene product performance specification of above-mentioned Catalyst Production.
Description of drawings
Fig. 1 is a process flow diagram of the present invention
Fig. 2 be in Fig. 1 spray-dryer the atomizing disk structural representation wherein,
The comprehensive still 2-of 1-colloidal mill 3-slurry tank 4-spray-dryer
The curved cylinder of 5-stoving oven 6-cyclonic separation 7-atomizing disk 8-
Slit 10 charging openings between the curved cylinder of 9-
Embodiment
Now the present invention is further described as follows with embodiment in conjunction with the accompanying drawings:
Embodiment 1
(1) prepares modification sol referring to the described method of CN1657571A, the pure water that takes by weighing 10.7 kilograms adds in the comprehensive still 1 of the stainless steel that is provided with electric mixer and steam jacket of 80 liters, add 1% peregal water phase surfactant mixture (properties-correcting agent again in this still, as follows), behind each 0.5 kilogram of 25～28% chemical pure ammoniacal liquor, start described electric mixer, with 6.67 kilograms silica weight percentage compositions is after 15% wet silicon gel slowly adds in the above-mentioned still, open steam cock and carry out the time constant-temperature heating, constant temperature timing control actuator temperature is set at 90 ℃, and time set is 4 hours (this process is finished automatically).Feed temperature in the still is reduced to≤50 ℃, the acrylic acid solution 1.5 kilograms (properties-correcting agent) with improving agent 80～90% adds in the reactor then, and the short period of time is put into container with this material after stirring, and just makes through colloidal sol (SiO aging and the adding additive modification
2Weight percentage is 5%) 20 kilograms.
(2) be that 5% silicon dioxide gel is through comprehensive still 1 with 20 kilograms above-mentioned weight percentage, be added in the colloidal mill 2, add urea modifier again, its add-on is 20 grams, through fragmentation, refinement and emulsification are delivered in the slurry tank 3 after 3 minutes, send the atomizing disk 7 (its rotating speed is 8500 rev/mins) of 10～12 curved cylinders 8 that spray-dryer 4 tops are provided with again through charging opening 10 by pump, described slurry from the slit 9 of 8 on atomizing disk 7 curved cylinders with the linear velocity of 45.8 meter per seconds, with from its below (atomizing disk 7 belows, as follows) from the temperature of spray-dryer 4 upper lateral part tangent line ingress 350 ℃ hot blast (150 ℃ of temperature of outgoing airs) together, at a high speed spirally in the same way be rotated down motion, the spray-dried device 4 bottom cones of fine particle one side outlet enters primary cyclone 6, the fine particle microspheroidal silicon-dioxide that comes out by these primary cyclone 6 bottoms, the macrobead microspheroidal silicon-dioxide (the two mixes the back water content is 4.5%) that comes out with spray-dryer 4 bottoms enters in the stoving oven 5, under 600 ℃, carry out roasting, promptly make microspheroidal silicon-dioxide, relevant datas such as its size-grade distribution see Table 1.
(1) produces SiO referring to the step (1) of embodiment 1
2The solid weight percentage composition is 20 kilograms of 9% colloidal sols.
(2) colloidal sol of 20 kilogram of 9% solid silica that above-mentioned steps (1) is made is through comprehensive still 1, be added in the colloidal mill 2, add urea modifier 100 grams again, through fragmentation, refinement and emulsification are delivered in the slurry tank 3 after 5 minutes, send into the atomizing disk 7 (its rotating speed is 9000 rev/mins) of 10～12 curved cylinders 8 that spray-dryer 4 tops are provided with by pump through adding inlet 10 again, described slurry from the slit 9 of 8 on the curved cylinder of atomizing disk with the linear velocity of 58.9 meter per seconds, with the hot blast (160 ℃ of temperature of outgoing airs) that from its below (atomizing disk 7 belows) temperature is 370 ℃ in spray-dryer 4 upper lateral part tangent line ingress, at a high speed spirally in the same way be rotated down motion, the spray-dried device 4 bottom cones of fine particle one side outlet enters primary cyclone 6, the fine particle microspheroidal silicon-dioxide that comes out by these primary cyclone 6 bottoms, the macrobead microspheroidal silicon-dioxide (the two mixes the back water content is 4.2%) that goes out rice with spray-dryer 4 bottoms enters in the stoving oven 5, under 600 ℃, carry out roasting, promptly make microspheroidal silicon-dioxide, relevant datas such as its size-grade distribution see Table 1.
(1) produces SiO referring to the step (1) of embodiment 1
2The solid weight percentage composition is 20 kilograms of 10% colloidal sols.
(2) colloidal sol that is 10% solid silica with 20 kilograms of above-mentioned weight percentages is through comprehensive still 1, be added in the colloid body mill 2, add urea modifier 120 grams again, through fragmentation, refinement and emulsification are delivered in the slurry tank 3 after 10 minutes, add inlet 10 through sending into the atomizing disk 7 (its rotating speed is 10000 rev/mins) of 10～12 curved cylinders 8 that spray dried machine 4 center of top are provided with by pump again, described slurry from the slit 9 of 8 on atomizing disk 7 curved cylinders with the linear velocity of 72 meter per seconds, with coming its below (atomizing disk below) temperature in spray-dryer 4 upper lateral part tangent line ingress of rotation is 380 ℃ hot blast (170 ℃ of temperature of outgoing airs), at a high speed spirally in the same way be rotated down motion, the spray-dried device 4 bottom cones of fine particle one side outlet enters primary cyclone 6, the fine particle microspheroidal silicon-dioxide that comes out by these primary cyclone 6 bottoms, the macrobead microspheroidal silicon-dioxide (the two mixes the back water content is 3%) that comes out with spray-dryer 4 bottoms enters in the stoving oven 5, under 600 ℃, carry out roasting, promptly make microspheroidal silicon-dioxide, relevant datas such as its size-grade distribution see Table 1.
(1) produces SiO referring to the step (1) of embodiment 1
2The solid weight percentage composition is 20 kilograms of 12% colloidal sols.
(2) colloidal sol that is 12% solid silica with 20 kilograms of above-mentioned weight percentages is through comprehensive still 1, be added in the colloid body mill 2, add urea modifier 130 grams again, through fragmentation, refinement and emulsification are delivered in the slurry tank 3 after 15 minutes, send into the atomizing disk 7 (its rotating speed is 12000 rev/mins) of 10～12 curved cylinders 8 that spray-dryer 4 center of top are provided with by pump through adding inlet 10 again, described slurry from the slit 9 of 8 on atomizing disk 7 curved cylinders with the linear velocity of 78.5 meter per seconds, with the hot blast (175 ℃ of temperature of outgoing airs) that from its below (atomizing disk 7 belows) temperature is 390 ℃ in the tangent line ingress of spray-dryer 4 upper lateral parts, be rotated down motion to speed is spiral in the same way, the spray-dried device 4 bottom cones of fine particle one side outlet enters primary cyclone 6, the fine particle microspheroidal silicon-dioxide that comes out by these primary cyclone 6 bottoms, the macrobead microspheroidal silicon-dioxide (the two mixes the back water content is 2.1%) that comes out with spray-dryer 4 bottoms enters in the stoving oven 5, under 600 ℃, carry out drying, promptly make microspheroidal silicon-dioxide, its key technical indexes relevant data sees Table 1.
(1) produces SiO referring to the step (1) of embodiment 1
2The solid weight percentage composition is 20 kilograms of 15% colloidal sols.
(2) colloidal sol that is 15% solid silica with 20 kilograms of above-mentioned weight percentages is through comprehensive still 1, be added in the colloid body mill 2, add urea modifier 150 grams again, through fragmentation, refinement and emulsification are delivered in the slurry tank 3 after 20 minutes, send into the atomizing disk 7 (its rotating speed is 14000 rev/mins) of 10～12 curved cylinders 8 that spray-dryer 4 center of top are provided with by pump through adding inlet 10 again, described slurry is from the linear velocity of slit 9 between atomizing disk 7 curved cylinders with 91.63 meter per seconds, with the hot blast (180 ℃ of temperature of outgoing airs) that from its below (atomizing disk 7 belows) temperature is 400 ℃ in spray-dryer 4 upper lateral part tangent line ingress, at a high speed spirally in the same way be rotated down motion, the spray-dried device 4 bottom cones of fine particle one side outlet enters primary cyclone 6, the fine particle microspheroidal silicon-dioxide that comes out by these primary cyclone 6 bottoms, the macrobead microspheroidal silicon-dioxide (the two mixes the back water content is 1.0%) that comes out with spray-dryer 4 bottoms enters in the stoving oven 5, under 600 ℃, carry out drying, promptly make microspheroidal silicon-dioxide, relevant datas such as its size-grade distribution see Table 1.
The selected spray-dryer of the present invention, its specification is: body internal diameter 3m, the high 3m of straight tube; Atomizing disk diameter 125mm, 8500～14000 rev/mins of rotating speeds, linear velocity 45.8～91.63 meter per seconds.Type of heating: fuel oil indirect heating air, 350～400 ℃ of hot blast temperatures, 150～180 ℃ of temperature of outgoing airs.
The specification of the microspheroidal silicon-dioxide that table 1. embodiment of the invention 1～5 makes
Example 6 (Preparation of Catalyst).
Take by weighing 1～5 prepared microspheroidal silica 1 10Kg by embodiment, put into the fluidized-bed activation furnace, use the nitrogen fluidisation, 600 ℃ of activation temperatures, 2 hours residence time will activate the back material and send in the reactor, and pack in advance 2 cubic metres different of this still defended hydroxyl in the triethyl aluminum desiliconization glue of alkane and 5Kg, drain dry after, put into mother liquor (TiCl again
3: MgCl
2: THF=1: 1.3: 120) 1.5 cubic metres, stir half an hour, drain dry after, use 25 kilograms of 10 kilograms of aluminium diethyl monochlorides and tri-n-hexyl aluminums again, add 1.5 cubic metres of different alkane of defending and reduce, after draining, promptly get the about 180Kg of catalyzer, produce 4 batches altogether.
The catalyzer that makes is above used on 300,000 tons of LLDPE full scale plants of the subordinate of China National Petroleum Corp., and its processing parameter is:
Reaction pressure 2.15MPaG
87.5 ℃ of temperature of reaction
Vinyl group dividing potential drop 0.65～0.75MPaG
Triethyl aluminum concentration 350ppm
Static-0.01KV
During ethylene feed 30T/
Hydrogen add-on 5.5Kg/
During butylene add-on 2.48t/
The application manipulate is steady, can satisfy the ordinary production needs with the catalyzer of above-mentioned microspheroidal silica supports production, the catalyzer that alternative import silica-gel carrier is produced; Catalyzer with the production of above-mentioned microspheroidal silica supports is operated good fluidity under condensing state, no plugging phenomenon takes place; Show the catalyzer of producing with the microspheroidal silica supports of method production of the present invention through application testing, its activity is about 4000～4500KgPE/Kg catalyzer (originally used activity of such catalysts 3800～4500KgPE/Kg), tap density 365Kg/m
2(originally used catalyst buildup density 320～340Kg/m
2) about; During the application, above-mentioned catalyzer and butene-1 responsiveness are normal; The LLDPE powder product performance test shows that obtains has reached the national product quality standard with the PFDA-7042 trade mark linear low density polyethylene product performance specification of above-mentioned Catalyst Production.
Equipment such as the used colloidal mill of the present invention, stoving oven and needed raw material are bought from the market.
Embodiment 6 (realizing preparation method's devices needed of microsphere silicon dioxide carrier on gas-phase fluidized bed by polyvinyls catalyst)
From Fig. 1 as seen, spray-dryer 4 usefulness pipelines of the present invention link to each other with slurry tank 3 by pump, and with same mode of connection, slurry tank 3 is connected with colloidal mill 2, and colloidal mill 2 links to each other with comprehensive still 1; Cone one side of spray-dryer 4 is connected with primary cyclone 6 with pipeline, and these cyclonic separator 6 lower end outlet pipes link to each other with spray-dryer 4 lower end outlet pipes; And spray-dryer 4 outlet pipes link to each other with stoving oven 6.From Fig. 1 and Fig. 2 as seen, be positioned at spray-dryer 4 center upper portion and be provided with atomizing disk 7, its periphery is provided with 10～18 curved cylinders 8, is equipped with the slit 9 of feed slurry ejection between each curved cylinder 8; The charging opening 10 that described atomizing disk 7 upper ends have slip to enter: atomizing disk 7 links to each other with axle whistle notch portion with whistle mouth axle sleeve, is positioned at the axle fixed by nut of atomizing disk 7 belows, and with carrying on the back cap (adding a nut again) fastening (not drawing among the figure).Below spray-dryer 4 upper lateral parts are positioned at atomizing disk 7, be provided with the tangent line inlet (Fig. 1 does not draw) that hot wind supply enters.Those skilled in the art can clearly directly derive the structure of the part of not drawing from the above description.
Claims (6)
1, the preparation method of gas-phase fluidized-bed ethylene rolymerization catalyst microspheric silica supports, colloidal sol after will handling through modification adds in the colloidal mill (2), wherein the silica solid weight percentage is 5～25%, add urea modifier again, its consumption is 0.1～2% of a colloidal sol weight, fragmentation by 3～20 minutes, after refinement and the emulsification, the rotating speed that enters spray-dryer (4) is 8500～14000 meters/minute a centrifugal spraying dish (7), and with the linear velocity of 45.8 meter per seconds～91.63 meter per seconds, with from described spray-dryer (5) upper lateral part, be positioned at atomizing disk (7) below temperature and be 340～400 ℃ hot blast together, at a high speed spirally in the same way be rotated down motion, spray-dried device (4) bottom cone one side outlet enters primary cyclone (6), the microspheric silicon-dioxide that bottom this cyclonic separator (6), comes out, the microspheric silicon-dioxide that comes out with spray-dryer (4) bottom enters in the stoving oven (7), in 600 ℃ of following roastings 1.5～2.5 hours, make microspheroidal silicon-dioxide, its the key technical indexes is: size-grade distribution d5030.15～48.59 μ m, d109.23～21.97 μ m, d9052.37～75.59 μ m; Tap density 0.29～0.32g/ml, specific surface area 297.2～310.2m2/g, pore volume 1.57～1.64ml/g, mean pore size 200 dusts ± 20 dusts.
2, method according to claim 1, the linear velocity that it is characterized in that described hot blast is 10～20 meter per seconds.
3, method according to claim 1, it is characterized in that described microspheric silicon-dioxide in stoving oven in 600 ℃ of following roastings 2 hours.
4, realize the needed spray-dryer of the described method of claim 1～3, the atomizing disk that it is characterized in that described spray-dryer top, its periphery is provided with 10～18 curved cylinders (8), is provided with the slit (9) for the colloidal sol ejection between each curved cylinder (8).
5, spray-dryer according to claim 4 is characterized in that this spray-dryer upper lateral part is positioned at the atomizing disk below, is provided with the tangent line inlet that hot wind supply enters.
6, spray-dryer according to claim 4, it is characterized in that spray-dryer cone one side is provided with primary cyclone (6), it links to each other with described spray-dryer cone by pipeline, and its lower end outlet links to each other with spray-dryer (4) lower end outlet pipe with pipeline.
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| CN110327852A (en) * | 2019-07-06 | 2019-10-15 | 江西奕方农业科技有限公司 | Colloidal sol equipment and its manufacturing method |
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| CN101363630B (en) * | 2008-08-29 | 2011-03-16 | 无锡雪浪输送机械有限公司 | Improved novel atomization plate |
| CN102773045A (en) * | 2012-06-29 | 2012-11-14 | 常州环生科创石墨设备有限公司 | Spray roasting device |
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| JPH0699135B2 (en) * | 1989-02-20 | 1994-12-07 | 富士デヴィソン株式会社 | Manufacturing method of spherical silica gel |
| US5348163A (en) * | 1993-01-19 | 1994-09-20 | Cabot Corporation | Method and apparatus for separating fine particles |
| US6313061B1 (en) * | 1998-12-22 | 2001-11-06 | W. R. Grace & Co.-Conn. | Method of making frangible spray dried agglomerated supports and olefin polymerization catalysts supported thereon |
| CN1158310C (en) * | 2001-09-03 | 2004-07-21 | 中国石油天然气股份有限公司 | Prepn of silica gel carrier |
| CN1216081C (en) * | 2002-04-19 | 2005-08-24 | 天津天大天海科技发展有限公司 | Ethylene polymerization and copolymerization catalyst preparing process |
| JP3936652B2 (en) * | 2002-11-11 | 2007-06-27 | 株式会社荏原製作所 | Method and apparatus for separating solid particles from suspension |
| CN1288079C (en) * | 2004-02-17 | 2006-12-06 | 吉林市吉清科技开发有限公司 | Preparation method of microspherical silica used as alkene polymerization catalyst carrier |
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| CN110327852A (en) * | 2019-07-06 | 2019-10-15 | 江西奕方农业科技有限公司 | Colloidal sol equipment and its manufacturing method |
| CN110327852B (en) * | 2019-07-06 | 2022-07-12 | 江西奕方农业科技有限公司 | Sol device and method for manufacturing the same |
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