CN111574320A - Method and system for preparing polychloropropene by dechlorinating polychloropropane - Google Patents
Method and system for preparing polychloropropene by dechlorinating polychloropropane Download PDFInfo
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- CN111574320A CN111574320A CN202010417914.3A CN202010417914A CN111574320A CN 111574320 A CN111574320 A CN 111574320A CN 202010417914 A CN202010417914 A CN 202010417914A CN 111574320 A CN111574320 A CN 111574320A
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- 238000000034 method Methods 0.000 title claims abstract description 57
- 230000000382 dechlorinating effect Effects 0.000 title claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 146
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 124
- 238000006243 chemical reaction Methods 0.000 claims abstract description 111
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 62
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 59
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 59
- 239000002131 composite material Substances 0.000 claims abstract description 55
- 238000007033 dehydrochlorination reaction Methods 0.000 claims abstract description 50
- 239000001301 oxygen Substances 0.000 claims abstract description 47
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 47
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000007788 liquid Substances 0.000 claims abstract description 41
- 230000004913 activation Effects 0.000 claims abstract description 34
- 230000008569 process Effects 0.000 claims abstract description 19
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical class CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 239000006200 vaporizer Substances 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 9
- 230000009471 action Effects 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 7
- 229910052718 tin Inorganic materials 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000006298 dechlorination reaction Methods 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- UTACNSITJSJFHA-UHFFFAOYSA-N 1,1,1,3-tetrachloropropane Chemical compound ClCCC(Cl)(Cl)Cl UTACNSITJSJFHA-UHFFFAOYSA-N 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 20
- UMGQVBVEWTXECF-UHFFFAOYSA-N 1,1,2,3-tetrachloroprop-1-ene Chemical compound ClCC(Cl)=C(Cl)Cl UMGQVBVEWTXECF-UHFFFAOYSA-N 0.000 claims description 16
- JFEVIPGMXQNRRF-UHFFFAOYSA-N 1,1,3-trichloroprop-1-ene Chemical compound ClCC=C(Cl)Cl JFEVIPGMXQNRRF-UHFFFAOYSA-N 0.000 claims description 16
- ZXPCCXXSNUIVNK-UHFFFAOYSA-N 1,1,1,2,3-pentachloropropane Chemical compound ClCC(Cl)C(Cl)(Cl)Cl ZXPCCXXSNUIVNK-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 10
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 10
- 230000008016 vaporization Effects 0.000 claims description 9
- 238000009834 vaporization Methods 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- 230000009849 deactivation Effects 0.000 claims 1
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 230000002779 inactivation Effects 0.000 abstract description 7
- 230000008929 regeneration Effects 0.000 abstract description 5
- 238000011069 regeneration method Methods 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000000571 coke Substances 0.000 abstract description 3
- 239000010453 quartz Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 238000004817 gas chromatography Methods 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- FEKGWIHDBVDVSM-UHFFFAOYSA-N 1,1,1,2-tetrachloropropane Chemical compound CC(Cl)C(Cl)(Cl)Cl FEKGWIHDBVDVSM-UHFFFAOYSA-N 0.000 description 1
- LIPPKMMVZOHCIF-UHFFFAOYSA-N 1,1,2-trichloroprop-1-ene Chemical compound CC(Cl)=C(Cl)Cl LIPPKMMVZOHCIF-UHFFFAOYSA-N 0.000 description 1
- GMWHTUNMFTUKHH-NDUABGMUSA-N 2-[2-(2-methoxyethoxy)ethoxy]ethyl (e)-2-cyano-3-(6-piperidin-1-ylnaphthalen-2-yl)prop-2-enoate;hydrochloride Chemical compound Cl.C1=CC2=CC(/C=C(C(=O)OCCOCCOCCOC)\C#N)=CC=C2C=C1N1CCCCC1 GMWHTUNMFTUKHH-NDUABGMUSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- -1 for example Chemical compound 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/92—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/12—Treating with free oxygen-containing gas
- B01J38/14—Treating with free oxygen-containing gas with control of oxygen content in oxidation gas
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
-
- 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
- Y02P20/584—Recycling of catalysts
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method and a system for preparing polychlorinated propylene by dechlorinating polychlorinated propane, which comprises a feed pump, a preheater, a vaporizer, a fixed bed reactor, a condenser gas-liquid separator and a product tank which are sequentially connected by pipelines, wherein the input pipeline of the feed pump is provided with a nitrogen and oxygen input device; the invention takes the polychloropropane as the raw material, and the polychloropropene is produced by dehydrochlorination under the action of the catalyst; the catalyst is a compound containing three or more metal oxides of Zr, Sn, Zn, Cu and Mg, and specifically comprises the processes of catalyst activation, dechlorination reaction of polychloropropane, product separation and rectification. The catalyst has good stability, and can continuously introduce nitrogen and oxygen in the reaction process, so that tar and coke generated on the surface of the composite metal oxide catalyst can be oxidized in time to avoid inactivation to influence the reaction process; the method can ensure that the catalyst can run for more than 10000h cumulatively, has good regeneration performance, can be recycled, and greatly saves the production cost.
Description
Technical Field
The invention belongs to the technical field of chlorinated olefin preparation, and particularly relates to a method and a system for preparing polychloropropene by dehydrochlorination of polychloropropane.
Background
The polychloropropene is an important industrial raw material, can also be used as an intermediate for synthesizing certain important raw materials, and is widely applied to a plurality of fields. Such as 2,3,3, 3-tetrafluoropropene (HFO-1234 yf), has good performance, very low ozone depletion index and low greenhouse gas effect index, and can simultaneously meet the low ozone depletion standard and reduce the global warming tendency, while 1,1, 3-trichloropropene and 1,1,2, 3-tetrachloropropene are important intermediates for synthesizing 2,3,3, 3-tetrafluoropropene, and therefore the preparation process thereof needs to be intensively researched and developed.
At present, the polychloropropene is mainly prepared by dehydrochlorination of chloropropane, for example, 1,1,1, 3-tetrachloropropane is prepared by dehydrochlorination of 1,1,1, 3-tetrachloropropane by reaction with alkali liquor under the action of phase transfer catalyst, and CN103119005A and CN105026346A disclose liquid-phase dehydrochlorination techniques of 1,1,1, 3-tetrachloropropane catalyzed by aluminum trichloride and ferric trichloride, respectively; CN106458799A discloses a method for preparing 1,1,2, 3-tetrachloropropene by liquid-phase dehydrochlorination of 1,1,1,2, 3-pentachloropropane (HCC-240 db) under the action of ferric chloride; the method is easy to generate serious 'three wastes' problem, is not beneficial to industrialized production, is easy to generate tar due to high catalyst activity, and is difficult to separate the catalyst after the reaction of the homogeneous catalyst; CN104163750A discloses a method for synthesizing 1,1,2, 3-tetrachloropropene by mixing and reacting trichloropropene, hydrogen chloride and oxygen under the action of an oxychlorination catalyst; the method has the advantages of low selectivity, severe equipment corrosion and short service life of the used catalyst, and is not beneficial to practical production and application. CN110511112A discloses a gas phase 1,1,1, 3-tetrachloropropane empty tube cracking technology, but the reaction temperature is high, coking is easy to generate, and the selectivity of the product is low. Therefore, it is necessary to synthesize polychloropropene by selecting a dechlorination catalyst for polychloropropane, which is easy to separate, has high selectivity and long life.
Disclosure of Invention
The invention aims to provide a method and a system for preparing polychloropropene by dehydrochlorination of polychloropropane, aiming at the defects of the prior art.
The invention adopts the following technical scheme:
a method for preparing polychlorinated propylene by dechlorinating polychlorinated propane, which takes the polychlorinated propane as a raw material and produces the polychlorinated propylene by the dehydrochlorination under the action of a catalyst; the catalyst is a composite metal oxide catalyst.
Further, the catalyst is a compound containing three or more of metal oxides of Zr, Sn, Zn, Cu, Ti and Mg.
Further, the catalyst is (ZrO)2)x(TO2)y(MO)zWhen expressed, x is 0-0.6, y is 0-0.5, z is 0-0.5, wherein T is Ti or Sn, and M is Zn, Cu or Mg.
Further, the method comprises the following steps:
s1, activation of the catalyst:
loading the catalyst into a fixed bed reactor, introducing 10% oxygen-poor nitrogen, heating, activating the catalyst at a certain temperature, and cooling to the required reaction temperature under the protection of nitrogen after the catalyst is activated;
s2, dehydrochlorination of polychlorinated propane:
the method comprises the following steps of (1) enabling the polychloropropane to enter a preheater through a metering pump for preheating, then entering a vaporizer for vaporization, and finally entering a fixed bed reactor for dehydrochlorination reaction under the catalysis of a catalyst;
s3, product separation:
the reacted materials pass through a condenser and a gas-liquid separator in sequence, and liquid reaction mixed materials are separated;
s4, product rectification:
rectifying and separating the liquid reaction mixture to obtain the polychloropropene.
Further, in S2, in the process of the dehydrochlorination of the polychloropropane, nitrogen and oxygen are continuously introduced to the surface of the composite metal oxide catalyst in the fixed bed reactor, so that tar generated on the surface of the composite metal oxide catalyst can be oxidized in time, and the reaction process is prevented from being influenced by the inactivation of the catalyst.
Further, the concentration of the oxygen in the reactor is kept between 2 and 3 percent.
Further, in S1, the activation temperature of the catalyst is 350-550 ℃, and the space velocity of the oxygen-poor nitrogen is 100-500 h-1And the activation time is 4-20 h.
Further, in S2, the mass space velocity of the polychlorinated propane feed is 1-5 h-1The preheating temperature is 120-150 ℃, and the vaporization temperature is 180-220 ℃.
Further, in S2, the dehydrochlorination reaction temperature is 200-300 ℃, and the reaction pressure is 0.1-0.3 MPa.
Furthermore, the invention controls the conversion rate of the polychloropropane to be 20-40% and the selectivity of the polychloropropene to be 95-99%.
Furthermore, the method can be used for catalyzing dehydrochlorination of 1,1,1,2, 3-pentachloropropane to produce 1,1,2, 3-tetrachloropropene; or the method is used for catalyzing dehydrochlorination of 1,1,1, 3-tetrachloropropane to produce 1,1, 3-trichloropropene.
The invention also provides a system for preparing the polychloropropene by dechlorinating the polychloropropane, which comprises a feeding pump, a preheater, a vaporizer, a fixed bed reactor, a condenser, a gas-liquid separator and a product tank which are sequentially connected by pipelines, wherein the feeding pump is provided with a nitrogen input device and an oxygen input device on an input pipeline, and is correspondingly provided with a nitrogen flowmeter and an oxygen flowmeter so as to control the flow of the nitrogen and the oxygen; the device is also provided with a buffer tank and an HCl absorption tank, wherein the buffer tank is connected with the gas-liquid separator through a pipeline, and the HCl absorption tank is connected with the buffer tank through a pipeline; the polychloropropane enters a system through a feed pump, is preheated through a preheater, then enters a vaporizer for vaporization, and finally enters a fixed bed reactor for dehydrochlorination reaction; the mixed solution after reaction sequentially enters a condenser and a gas-liquid separator for condensation and gas-liquid separation; hydrogen chloride gas separated by the gas-liquid separator enters a buffer tank and is then recovered; the reaction liquid separated by the gas-liquid separator enters a product tank, and then is rectified and separated to obtain the target product, namely the polychloropropene.
The invention has the beneficial effects that:
(1) according to the invention, the composite metal oxide catalyst is fixed in the fixed bed reactor, the polychlorinated propane is catalyzed to perform gas-phase dehydrochlorination to prepare the polychlorinated propylene, the gaseous polychlorinated propylene is condensed and separated, and the target product is naturally separated from the catalyst, so that the problem that the homogeneous catalyst is difficult to separate in the prior art is solved;
(2) the composite metal oxide catalyst has good stability and high strength, and nitrogen and oxygen are continuously introduced in the reaction process, wherein the nitrogen can be used for diluting organic gas in a reactor, so that the self-polymerization of the polychloropropene in the reactor is reduced; on one hand, the low-concentration oxygen can timely oxidize and remove tar generated on the surface of the composite metal oxide catalyst, prevent the catalyst from being deactivated to influence the reaction process, reduce the replacement frequency of the catalyst, and on the other hand, a small amount of oxygen can also inhibit the self-polymerization of the polychloropropene and improve the selectivity of the polychloropropene; meanwhile, a small amount of oxygen in the reactor can not influence the product of the polychloropropene; by adopting the method, the catalyst can be operated for 10000-15000 h accumulatively, the activity of the catalyst is kept at 25-35% in the reaction process, the utilization efficiency of the catalyst is improved, and the service life of the catalyst is prolonged;
(3) the composite metal oxide catalyst has good selectivity, moderate catalyst activity, 20-40% of polychloropropane conversion rate, reduced olefin self-polymerization and high boiling point compound generation, and high selectivity of polychloropropene, which is more than 95% and can reach 99% at most;
(4) the composite metal oxide catalyst has good regeneration performance, the inactivated catalyst is easy to regenerate, and the catalytic activity is not reduced after regeneration; the composite metal oxide catalyst material is easy to obtain, low in price, capable of greatly saving the production cost and easy for industrial production.
Description of the drawings:
FIG. 1 is a schematic process flow diagram of the present invention for a polychloropropane;
the labels in the figures are: 1-nitrogen flow meter, 2-oxygen flow meter, 3-feeding pump, 4-preheater, 5-vaporizer, 6-fixed bed reactor, 7-condenser, 8-gas-liquid separator, 9-product tank, 10-buffer tank and 11-HCl absorption tank.
The specific implementation mode is as follows:
in order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
A method for preparing polychlorinated propylene by dechlorinating polychlorinated propane, which takes the polychlorinated propane as a raw material and produces the polychlorinated propylene by the dehydrochlorination under the action of a catalyst; the catalyst is a composite metal oxide catalyst; specifically, the catalyst is a compound containing three or more metal oxides of Zr, Sn, Zn, Cu, Ti and Mg; what is needed isThe catalyst is (ZrO)2)x(TO2)y(MO)zWhen expressed, x is 0-0.6, y is 0-0.5, z is 0-0.5, wherein T is Ti or Sn, and M is Zn, Cu or Mg.
The method comprises the following steps:
s1, activation of the catalyst:
loading the catalyst into a fixed bed reactor, introducing 10% oxygen-poor nitrogen, heating, activating the catalyst at a certain temperature, and cooling to the required reaction temperature under the protection of nitrogen after the catalyst is activated; the activation temperature of the catalyst is 350-550 ℃, and the air speed of nitrogen is 100-500 h-1And the activation time is 4-20 h.
S2, dehydrochlorination of polychlorinated propane:
the method comprises the following steps of enabling the polychloropropane to enter a preheater through a metering pump for preheating, then entering a vaporizer for vaporization, finally entering a fixed bed reactor, and carrying out dehydrochlorination reaction under the catalysis of a catalyst, wherein the polychloropropane conversion rate is controlled to be 20-40%; the mass airspeed of the polychlorinated propane feeding is 1-5 h-1Preheating at 120-150 ℃ and vaporizing at 180-220 ℃; the dehydrochlorination reaction temperature is 200-300 ℃, and the reaction pressure is 0.1-0.3 MPa.
It is noted that during the dechlorination reaction of the polychloropropane, nitrogen and oxygen are continuously introduced to the surface of the composite metal oxide catalyst in the fixed bed reactor, the nitrogen can be used for diluting the organic gas in the reactor, and the self-polymerization of the polychloropropene in the reactor is reduced; the concentration of oxygen in the reactor is kept at 2-3%, on one hand, tar generated on the surface of the composite metal oxide catalyst can be timely oxidized and removed, the catalyst is prevented from being inactivated to influence the reaction process, on the other hand, a small amount of oxygen can also inhibit the self-polymerization of the polychloropropene, and the selectivity of the polychloropropene is improved; meanwhile, a small amount of oxygen in the reactor does not influence the product of the polychloropropene, which is also proved in the actual production.
S3, product separation:
the reacted materials sequentially pass through a condenser and a gas-liquid separator, a liquid reaction mixed material is separated, and the selectivity of the polychloropropene is kept at 95-99%;
s4, product rectification:
rectifying and separating the liquid reaction mixture to obtain the polychloropropene.
The method can be widely applied to the preparation of the polychloropropene by the dehydrochlorination of the polychloropropane, and particularly applied to the production of the 1,1,2, 3-tetrachloropropene by catalyzing the dehydrochlorination of the 1,1,1,2, 3-pentachloropropane or the production of the 1,1, 3-trichloropropene by catalyzing the dehydrochlorination of the 1,1,1, 3-tetrachloropropane.
The invention also provides a system for preparing the polychloropropene by dechlorinating the polychloropropane, which comprises a feed pump 3, a preheater 4, a vaporizer 5, a fixed bed reactor 6, a condenser 7, a gas-liquid separator 8 and a product tank 9 which are sequentially connected by pipelines, wherein the input pipeline of the feed pump 3 is provided with a nitrogen input device and an oxygen input device, and a nitrogen flowmeter 1 and an oxygen flowmeter 2 are correspondingly arranged so as to control the flow of the nitrogen and the oxygen; the device is also provided with a buffer tank 10 and an HCl absorption tank 11, wherein the buffer tank 10 is connected with the gas-liquid separator 8 through a pipeline, and the HCl absorption tank 11 is connected with the buffer tank 10 through a pipeline; the polychloropropane enters the system through a feed pump 3, is preheated through a preheater 4, then enters a vaporizer 5 for vaporization, and finally enters a fixed bed reactor 6 for dehydrochlorination reaction; the mixed solution after reaction enters a condenser 7 and a gas-liquid separator 8 in sequence for condensation and gas-liquid separation; the hydrogen chloride gas separated by the gas-liquid separator 8 enters a buffer tank 10 and is then recovered; the reaction liquid separated by the gas-liquid separator 8 enters a product tank 9, and then is rectified and separated to obtain the polychloropropene.
Example 1
15g of fresh ZrO2the-ZnO-MgO composite metal oxide catalyst is loaded into a quartz reaction tube with the diameter of 20mm at the airspeed of 400h-1Introducing 10% oxygen-poor nitrogen, heating to 400 ℃ to activate the catalyst, wherein the activation time is 6 h; after the catalyst activation is completed, cooling to the required reaction temperature under the protection of nitrogen; 1,1,1, 3-tetrachloropropane is pumped by a high-pressure constant flow pump for 1.1h-1The mass space velocity of the material is that the material is preheated by a preheater at 120 ℃, vaporized at 180 ℃ and then enters into the reactionCracking at 210 deg.c and reaction pressure of 0.1 MPa; in the process of dehydrochlorination of 1,1,1, 3-tetrachloropropane, continuously introducing nitrogen and oxygen to the surface of the composite metal oxide catalyst in the fixed bed reactor, and keeping the concentration of the oxygen in the reactor at 2 percent, so that tar generated on the surface of the composite metal oxide catalyst can be oxidized in time, and the catalyst is prevented from being inactivated to influence the reaction process; the mixed gas generated in the reaction is condensed and separated by a condenser and a gas-liquid separator, then the sample is taken, the conversion rate of 1,1,1, 3-tetrachloropropane is 28.2 percent after the gas chromatography analysis reaction is carried out for 24 hours, and the selectivity of the polychloropropene is 98.9 percent; and carrying out reduced pressure rectification on the condensed and collected mixed solution under-0.10 MPa, and separating to obtain the polychloropropene product with the purity of 99.6 percent.
Example 2
15g of fresh ZrO2the-ZnO-CuO composite metal oxide catalyst is loaded into a quartz reaction tube with the diameter of 20mm, and the space velocity is 400h-1Introducing 10% oxygen-poor nitrogen, heating to 400 ℃ to activate the catalyst, wherein the activation time is 6 h; after the catalyst activation is completed, cooling to the required reaction temperature under the protection of nitrogen; 1,1,1, 3-tetrachloropropane is pumped by a high-pressure constant flow pump for 1.5h-1The mass space velocity of the method is that the material is preheated by a preheater at 120 ℃, vaporized at 190 ℃, enters a reactor and is cracked at 220 ℃, and the reaction pressure is 0.1 MPa; in the process of dehydrochlorination of 1,1,1, 3-tetrachloropropane, continuously introducing nitrogen and oxygen to the surface of the composite metal oxide catalyst in the fixed bed reactor, and keeping the concentration of the oxygen in the reactor at 2.5 percent, so that tar generated on the surface of the composite metal oxide catalyst can be oxidized in time, and the reaction process is prevented from being influenced by the inactivation of the catalyst; the mixed gas generated in the reaction is condensed and separated by a condenser and a gas-liquid separator, then the sample is taken, the conversion rate of 1,1,1, 3-tetrachloropropane is 30.8 percent after the gas chromatography analysis reaction is carried out for 24 hours, and the selectivity of 1,1, 3-trichloropropene is 98.2 percent; and (3) carrying out reduced pressure rectification on the condensed and collected mixed solution under the pressure of-0.10 MPa, and separating to obtain the 1,1, 3-trichloropropene product with the purity of 99.7%.
Example 3
15g of fresh ZrO2-ZnO-CuO-MgO composite metal oxide catalyst with a diameter of 20mmIn a quartz reaction tube, the space velocity is 400h-1Introducing 10% oxygen-poor nitrogen, heating to 400 ℃ to activate the catalyst, wherein the activation time is 6 h; after the catalyst activation is completed, cooling to the required reaction temperature under the protection of nitrogen; 1,1,1, 3-tetrachloropropane is pumped by a high-pressure constant flow pump for 2.0h-1The mass space velocity of the method is that the material is preheated by a preheater at 130 ℃, vaporized at 200 ℃, enters a reactor and is cracked at 230 ℃, and the reaction pressure is 0.1 MPa; in the process of dehydrochlorination of 1,1,1, 3-tetrachloropropane, continuously introducing nitrogen and oxygen to the surface of the composite metal oxide catalyst in the fixed bed reactor, and keeping the concentration of the oxygen in the reactor at 3 percent, so that tar generated on the surface of the composite metal oxide catalyst can be oxidized in time, and the catalyst is prevented from being inactivated to influence the reaction process; the mixed gas generated in the reaction is condensed and separated by a condenser and a gas-liquid separator, then the sample is taken, the conversion rate of 1,1,1, 3-tetrachloropropane is 36.7 percent after the gas chromatography analysis reaction is carried out for 24 hours, and the selectivity of 1,1, 3-trichloropropene is 98.6 percent; and (3) carrying out reduced pressure rectification on the condensed and collected mixed solution under the pressure of-0.10 MPa, and separating to obtain the 1,1, 3-trichloropropene product with the purity of 99.8%.
Example 4
15g of fresh ZrO2-SnO2the-CuO composite metal oxide catalyst is loaded into a quartz reaction tube with the diameter of 20mm, and the space velocity is 400h-1Introducing 10% oxygen-poor nitrogen, heating to 400 ℃ to activate the catalyst, wherein the activation time is 6 h; after the catalyst activation is completed, cooling to the required reaction temperature under the protection of nitrogen; 1,1,1, 3-tetrachloropropane is pumped by a high-pressure constant flow pump for 3.0h-1The mass space velocity of the method is that the material is preheated by a preheater at 140 ℃, vaporized at 210 ℃, enters a reactor and is cracked at 250 ℃, and the reaction pressure is 0.1 MPa; in the process of dehydrochlorination of 1,1,1, 3-tetrachloropropane, continuously introducing nitrogen and oxygen to the surface of the composite metal oxide catalyst in the fixed bed reactor, and keeping the concentration of the oxygen in the reactor at 2 percent, so that tar generated on the surface of the composite metal oxide catalyst can be oxidized in time, and the catalyst is prevented from being inactivated to influence the reaction process; the mixed gas generated by the reaction is condensed and separated by a condenser and a gas-liquid separator, then is sampled and is subjected to gas chromatographyAfter the separation reaction for 24 hours, the conversion rate of the 1,1,1, 3-tetrachloropropane is 33.4 percent, and the selectivity of the 1,1, 3-trichloropropene is 95.1 percent; and (3) carrying out reduced pressure rectification on the condensed and collected mixed solution under the pressure of-0.10 MPa, and separating to obtain the 1,1, 3-trichloropropene product with the purity of 99.7%.
Example 5
15g of fresh ZrO2-SnO2the-MgO composite metal oxide catalyst is loaded into a quartz reaction tube with the diameter of 20mm, and the space velocity is 400h-1Introducing 10% oxygen-poor nitrogen, heating to 400 ℃ to activate the catalyst, wherein the activation time is 6 h; after the catalyst activation is completed, cooling to the required reaction temperature under the protection of nitrogen; 1,1,1, 3-tetrachloropropane is pumped by a high-pressure constant flow pump for 4.0h-1The mass space velocity of the method is that the material is preheated by a preheater at 150 ℃, vaporized at 220 ℃, enters a reactor and is cracked at 270 ℃, and the reaction pressure is 0.1 MPa; in the process of dehydrochlorination of 1,1,1, 3-tetrachloropropane, continuously introducing nitrogen and oxygen to the surface of the composite metal oxide catalyst in the fixed bed reactor, and keeping the concentration of the oxygen in the reactor at 3 percent, so that tar generated on the surface of the composite metal oxide catalyst can be oxidized in time, and the catalyst is prevented from being inactivated to influence the reaction process; the mixed gas generated in the reaction is condensed and separated by a condenser and a gas-liquid separator, then the sample is taken, the conversion rate of 1,1,1, 3-tetrachloropropane is 35.2 percent after the gas chromatography analysis reaction is carried out for 24 hours, and the selectivity of 1,1, 3-trichloropropene is 95.5 percent; and (3) carrying out reduced pressure rectification on the condensed and collected mixed solution under the pressure of-0.10 MPa, and separating to obtain the 1,1, 3-trichloropropene product with the purity of 99.8%.
Example 6
15g of fresh ZrO2the-ZnO-MgO composite metal oxide catalyst is loaded into a quartz reaction tube with the diameter of 20mm at the airspeed of 200h-1Introducing 10% oxygen-poor nitrogen, heating to 400 ℃ to activate the catalyst, wherein the activation time is 6 h; after the catalyst activation is completed, cooling to the required reaction temperature under the protection of nitrogen; 1,1,1,2, 3-pentachloropropane is pumped by a high-pressure constant flow pump for 1.5h-1The mass space velocity of the method is that the material is preheated by a preheater at 120 ℃, vaporized at 220 ℃, enters a reactor and is cracked at 260 ℃, and the reaction pressure is 0.1 MPa; in the presence of 1,1,1,2, 3-pentachloropropaneIn the process of alkane dehydrochlorination, nitrogen and oxygen are continuously introduced to the surface of the composite metal oxide catalyst in the fixed bed reactor, the concentration of the oxygen in the reactor is kept at 2.7 percent, tar generated on the surface of the composite metal oxide catalyst can be oxidized in time, and the catalyst is prevented from being inactivated to influence the reaction process; the mixed gas generated in the reaction is condensed and separated by a condenser and a gas-liquid separator, then the mixed gas is sampled, the conversion rate of 1,1,1,2, 3-pentachloropropane is 25.2 percent after the gas chromatography analysis reaction is carried out for 24 hours, and the selectivity of 1,1,2, 3-tetrachloropropene is 98.9 percent; and (3) carrying out reduced pressure rectification on the condensed and collected mixed solution under-0.10 MPa, and separating to obtain the 1,1,2, 3-tetrachloropropene product with the purity of 99.8%.
Example 7
15g of fresh ZrO2the-ZnO-CuO composite metal oxide catalyst is loaded into a quartz reaction tube with the diameter of 20mm, and the space velocity is 300h-1Introducing 10% oxygen-poor nitrogen, heating to 400 ℃ to activate the catalyst, wherein the activation time is 4 h; after the catalyst activation is completed, cooling to the required reaction temperature under the protection of nitrogen; 1,1,1,2, 3-pentachloropropane is pumped by a high-pressure constant flow pump for 2.0h-1The mass space velocity of the method is that the material is preheated by a preheater at 120 ℃, vaporized at 210 ℃, enters a reactor and is cracked at 250 ℃, and the reaction pressure is 0.1 MPa; in the process of dehydrochlorination of 1,1,1,2, 3-pentachloropropane, continuously introducing nitrogen and oxygen to the surface of the composite metal oxide catalyst in the fixed bed reactor, and keeping the concentration of the oxygen in the reactor at 2.6 percent, so that tar generated on the surface of the composite metal oxide catalyst can be oxidized in time, and the reaction process is prevented from being influenced by the inactivation of the catalyst; the mixed gas generated in the reaction is condensed and separated by a condenser and a gas-liquid separator, then the mixed gas is sampled, the conversion rate of 1,1,1,2, 3-pentachloropropane is 34.8 percent after the gas chromatography analysis reaction is carried out for 24 hours, and the selectivity of 1,1,2, 3-tetrachloropropene is 98.8 percent; and (3) carrying out reduced pressure rectification on the condensed and collected mixed solution under-0.10 MPa, and separating to obtain the 1,1,2, 3-tetrachloropropene product with the purity of 99.8%.
Example 8
15g of fresh ZrO2the-ZnO-CuO-MgO composite metal oxide catalyst is loaded into a quartz reaction tube with the diameter of 20mm at the space velocity of 200h-1Introducing 10% oxygen-poor nitrogen, heating to 400 ℃ to activate the catalyst, wherein the activation time is 4 h; after the catalyst activation is completed, cooling to the required reaction temperature under the protection of nitrogen; 1,1,1,2, 3-pentachloropropane is pumped by a high-pressure constant flow pump for 3.0h-1The mass space velocity of the method is that the material is preheated by a preheater at 130 ℃, vaporized at 220 ℃, enters a reactor and is cracked at 270 ℃, and the reaction pressure is 0.1 MPa; in the process of dehydrochlorination of 1,1,1,2, 3-pentachloropropane, continuously introducing nitrogen and oxygen to the surface of the composite metal oxide catalyst in the fixed bed reactor, keeping the concentration of the oxygen in the reactor at 2.5%, so that tar generated on the surface of the composite metal oxide catalyst can be oxidized in time, and the reaction process is prevented from being influenced by the inactivation of the catalyst; the mixed gas generated in the reaction is condensed and separated by a condenser and a gas-liquid separator, then the mixed gas is sampled, the conversion rate of 1,1,1,2, 3-pentachloropropane is 35.3 percent after the gas chromatography analysis reaction is carried out for 24 hours, and the selectivity of 1,1,2, 3-tetrachloropropene is 98.7 percent; and (3) carrying out reduced pressure rectification on the condensed and collected mixed solution under-0.10 MPa, and separating to obtain the 1,1,2, 3-tetrachloropropene product with the purity of 99.8%.
Comparative example 1
17.6g of deactivated ZrO2the-ZnO-CuO-MgO composite metal oxide catalyst is loaded in a quartz reaction tube with the diameter of 20mm, and the space velocity is 400h-1Introducing 10% oxygen-poor nitrogen, heating to 350 ℃ to activate the catalyst, wherein the activation time is 20 h; after the catalyst activation is completed, cooling to the required reaction temperature under the protection of nitrogen; 1,1,1, 3-tetrachloropropane is pumped by a high-pressure constant flow pump for 2.0h-1The mass space velocity of the method is that the material is preheated by a preheater at 130 ℃, vaporized at 200 ℃, enters a reactor and is cracked at 230 ℃, and the reaction pressure is 0.1 MPa; in the process of dehydrochlorination of 1,1,1, 3-tetrachloropropane, continuously introducing nitrogen and oxygen to the surface of the composite metal oxide catalyst in the fixed bed reactor, and keeping the concentration of the oxygen in the reactor at 2 percent, so that tar generated on the surface of the composite metal oxide catalyst can be oxidized in time, and the catalyst is prevented from being inactivated to influence the reaction process; the mixed gas generated in the reaction is condensed and separated by a condenser and a gas-liquid separator, then the mixed gas is sampled, and the gas chromatography analysis is carried out to analyze the conversion rate of 1,1,1, 3-tetrachloropropane after 24 hours of reaction37.1 percent, and the selectivity of the 1,1, 3-trichloropropene is 98.2 percent; and (3) carrying out reduced pressure rectification on the condensed and collected mixed solution under the pressure of-0.10 MPa, and separating to obtain the 1,1, 3-trichloropropene product with the purity of 99.8%.
Comparative example 2
23g of deactivated ZrO2the-ZnO-CuO composite metal oxide catalyst is loaded into a quartz reaction tube with the diameter of 20mm at the space velocity of 200h-1Introducing 10% oxygen-poor nitrogen, heating to 350 ℃ to activate the catalyst, wherein the activation time is 20 h; after the catalyst activation is completed, cooling to the required reaction temperature under the protection of nitrogen; 1,1,1, 3-tetrachloropropane is pumped by a high-pressure constant flow pump for 2.0h-1The mass space velocity of the method is that the material is preheated by a preheater at 130 ℃, vaporized at 210 ℃, enters a reactor and is cracked at 250 ℃, and the reaction pressure is 0.1 MPa; in the process of dehydrochlorination of 1,1,1,2, 3-pentachloropropane, continuously introducing nitrogen and oxygen to the surface of the composite metal oxide catalyst in the fixed bed reactor, keeping the concentration of the oxygen in the reactor at 2.5%, so that tar generated on the surface of the composite metal oxide catalyst can be oxidized in time, and the reaction process is prevented from being influenced by the inactivation of the catalyst; the mixed gas generated in the reaction is condensed and separated by a condenser and a gas-liquid separator, then the mixed gas is sampled, the conversion rate of 1,1,1,2, 3-pentachloropropane is 35.5 percent after the gas chromatography analysis reaction is carried out for 24 hours, and the selectivity of 1,1,2, 3-tetrachloropropene is 98.4 percent; and (3) carrying out reduced pressure rectification on the condensed and collected mixed solution under-0.10 MPa, and separating to obtain the 1,1,2, 3-tetrachloropropene product with the purity of 99.8%.
Comparative example 3
15g of fresh ZrO2-SnO2the-CuO composite metal oxide catalyst is loaded into a quartz reaction tube with the diameter of 20mm, and the space velocity is 400h-1Introducing nitrogen, heating to 350 ℃ to activate the catalyst, wherein the activation time is 20 h; after the catalyst activation is completed, cooling to the required reaction temperature under the protection of nitrogen; 1,1,1, 3-tetrachloropropane is pumped by a high-pressure constant flow pump for 2.0h-1The mass space velocity of the method is that the material is preheated by a preheater at 130 ℃, vaporized at 200 ℃, enters a reactor and is cracked at 230 ℃, and the reaction pressure is 0.1 MPa; the mixed gas generated by the reaction is condensed by a condenser and a gas-liquid separatorAfter separation, sampling, and analyzing by gas chromatography, the conversion rate of 1,1,1, 3-tetrachloropropane is 8.7% and the selectivity of 1,1, 3-trichloropropene is 89.4% after 6h of reaction; and (3) carrying out reduced pressure rectification on the condensed and collected mixed solution under the pressure of-0.10 MPa, and separating to obtain the 1,1, 3-trichloropropene product with the purity of 99.3%.
Comparative example 4
15g of fresh ZrO2-SnO2the-CuO composite metal oxide catalyst is loaded into a quartz reaction tube with the diameter of 20mm, and the space velocity is 300h-1Introducing nitrogen, heating to 450 ℃ to activate the catalyst, wherein the activation time is 18 h; after the catalyst activation is completed, cooling to the required reaction temperature under the protection of nitrogen; 1,1,1,2, 3-pentachloropropane is pumped by a high-pressure constant flow pump for 2.5h-1The mass space velocity of the method is that the material is preheated by a preheater at 140 ℃, vaporized at 200 ℃, enters a reactor and is cracked at 260 ℃, and the reaction pressure is 0.1 MPa; the mixed gas generated in the reaction is condensed and separated by a condenser and a gas-liquid separator, then the sample is taken, the conversion rate of 1,1,1, 3-tetrachloropropane is 8.4 percent after the gas chromatography analysis reaction is carried out for 6 hours, and the selectivity of 1,1,2, 3-tetrachloropropene is 82.4 percent; and (3) carrying out reduced pressure rectification on the condensed and collected mixed solution under the pressure of-0.10 MPa, and separating to obtain the 1,1,2, 3-tetrachloropropene product with the purity of 99.0%.
From the above examples 1 to 8 and comparative examples 1 to 4, it can be seen that the deactivated composite metal oxide catalyst still has catalytic activity after being activated, and the composite metal oxide catalyst of the present invention can be recycled; comparative examples 3 to 4 in the dehydrochlorination reaction of polychloropropane, nitrogen and oxygen were not introduced to the surface of the composite metal oxide catalyst in the fixed bed reactor, resulting in a decrease in activity due to tar or coke generated on the surface of the composite metal oxide catalyst, a decrease in the conversion rate of tetrachloropropane, and a significant decrease in the selectivity of polychloropropene.
The invention uses the composite metal oxide catalyst to catalyze the gas-phase dehydrochlorination of the polychloropropane to prepare the polychloropropene, and can solve the problem of difficult separation of a homogeneous catalyst; the composite metal oxide catalyst has good stability, and the tar and coke generated on the surface of the composite metal oxide catalyst can be oxidized in time by continuously introducing nitrogen and oxygen in the reaction process, so that the reaction process is prevented from being influenced by the inactivation of the catalyst; by adopting the method, the catalyst can be operated for 10000-15000 h in an accumulated way, and the activity of the catalyst is kept at 25-35% in the reaction process; the catalyst has good regeneration performance, the inactivated catalyst is easy to regenerate, and the catalytic activity cannot be reduced after regeneration, which is also proved in the actual production, thereby greatly saving the production cost.
The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention, it should be noted that, for those skilled in the art, several modifications and decorations without departing from the principle of the present invention should be regarded as the protection scope of the present invention.
Claims (10)
1. A method for preparing polychlorinated propylene by dechlorinating polychlorinated propane is characterized in that the polychlorinated propane is used as a raw material, and the dechlorination is carried out under the action of a catalyst to produce the polychlorinated propylene; the catalyst is a composite metal oxide catalyst.
2. The process for the dehydrochlorination of polychloropropane to produce polychloropropene of claim 1 wherein the catalyst is a complex comprising three or more metal oxides of Zr, Sn, Zn, Cu, Ti and Mg.
3. The process for the dehydrochlorination of polychloropropane to polychloropropene of claim 2 wherein the catalyst is selected from the group consisting of (ZrO), poly (meth) acrylates2)x(TO2) y (MO) z represents x is 0-0.6, y is 0-0.5, z is 0-0.5, wherein T is Ti or Sn, and M is Zn, Cu or Mg.
4. The process for the dehydrochlorination of polychloropropane to polychloropropene of claim 1, comprising the steps of:
s1, activation of the catalyst:
loading the catalyst into a fixed bed reactor, introducing 10% oxygen-poor nitrogen, heating, activating the catalyst at a certain temperature, and cooling to the required reaction temperature under the protection of nitrogen after the catalyst is activated;
s2, dehydrochlorination of polychlorinated propane:
the method comprises the following steps of (1) enabling the polychloropropane to enter a preheater through a metering pump for preheating, then entering a vaporizer for vaporization, and finally entering a fixed bed reactor for dehydrochlorination reaction under the catalysis of a catalyst;
s3, product separation:
the reacted materials pass through a condenser and a gas-liquid separator in sequence, and liquid reaction mixed materials are separated;
s4, product rectification:
rectifying and separating the liquid reaction mixture to obtain the polychloropropene.
5. The method of claim 4, wherein in S2, during the dehydrochlorination reaction of the polychloropropane, nitrogen and oxygen are continuously introduced onto the surface of the composite metal oxide catalyst in the fixed bed reactor, so that the tar generated on the surface of the composite metal oxide catalyst can be oxidized in time, thereby preventing the deactivation of the catalyst from affecting the reaction process.
6. The process for the production of polychloropropene by dehydrochlorination of polychloropropane according to claim 5, wherein the oxygen concentration in the reactor is maintained between 2 and 3%.
7. The method for preparing polychloropropene by dehydrochlorination of polychloropropane according to claim 4, wherein the activation temperature of the catalyst in S1 is 350-550 ℃, and the space velocity of oxygen-poor nitrogen gas is 100-500 h-1And the activation time is 4-20 h.
8. The process for preparing polychloropropene by dehydrochlorination of polychloropropane according to claim 4, wherein the mass space velocity of the polychloropropane feed in S2 is 1-5 h-1Before, inThe heat temperature is 120-150 ℃, and the vaporization temperature is 180-220 ℃; the dehydrochlorination reaction temperature is 200-300 ℃, and the reaction pressure is 0.1-0.3 MPa.
9. The process for the preparation of polychloropropene by dehydrochlorination of polychloropropane according to any of claims 1 to 7, wherein the process is useful for catalyzing the dehydrochlorination of 1,1,1,2, 3-pentachloropropane to 1,1,2, 3-tetrachloropropene; or the method is used for catalyzing dehydrochlorination of 1,1,1, 3-tetrachloropropane to produce 1,1, 3-trichloropropene.
10. The system for preparing the polychloropropene by dechlorinating the polychloropropane is characterized by comprising a feeding pump (3), a preheater (4), a vaporizer (5), a fixed bed reactor (6), a condenser (7), a gas-liquid separator (8) and a product tank (9) which are sequentially connected by pipelines, wherein a nitrogen input device and an oxygen input device are arranged on an input pipeline of the feeding pump (3), and a nitrogen flowmeter (1) and an oxygen flowmeter (2) are correspondingly arranged so as to control the flow rates of the nitrogen and the oxygen; the device is also provided with a buffer tank (10) and an HCl absorption tank (11), wherein the buffer tank (10) is connected with the gas-liquid separator (8) through a pipeline, and the HCl absorption tank (11) is connected with the buffer tank (10) through a pipeline; the polychloropropane enters a system through a feed pump (3), is preheated through a preheater (4), then enters a vaporizer (5) for vaporization, and finally enters a fixed bed reactor (6) for dehydrochlorination reaction; the mixed solution after reaction sequentially enters a condenser (7) and a gas-liquid separator (8) for condensation and gas-liquid separation; the hydrogen chloride gas separated by the gas-liquid separator (8) enters a buffer tank (10) and is then recovered; the reaction liquid separated by the gas-liquid separator (8) enters a product tank (9), and then is rectified and separated to obtain the polychloropropene.
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| CN101754941A (en) * | 2007-07-25 | 2010-06-23 | 霍尼韦尔国际公司 | Processes for preparing 1,1,2,3-tetrachloropropene |
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| CN110573482A (en) * | 2017-06-30 | 2019-12-13 | 中央硝子株式会社 | Preparation method of 1-chloro-3, 3, 3-trifluoropropene |
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| CN101754941A (en) * | 2007-07-25 | 2010-06-23 | 霍尼韦尔国际公司 | Processes for preparing 1,1,2,3-tetrachloropropene |
| CN108026001A (en) * | 2015-09-21 | 2018-05-11 | 阿科玛股份有限公司 | The method that tetrachloropropylene is prepared by the catalyzed gas dehydrochlorination of pentachloropropane |
| CN109311785A (en) * | 2016-06-23 | 2019-02-05 | 蓝立方知识产权有限责任公司 | The dehydrochlorination method of chloralkane |
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Application publication date: 20200825 |