CN101293637A - Apparatus and method for producing chlorine gas with hydrogen chloride catalytic oxidation - Google Patents
Apparatus and method for producing chlorine gas with hydrogen chloride catalytic oxidation Download PDFInfo
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- CN101293637A CN101293637A CNA2008101156952A CN200810115695A CN101293637A CN 101293637 A CN101293637 A CN 101293637A CN A2008101156952 A CNA2008101156952 A CN A2008101156952A CN 200810115695 A CN200810115695 A CN 200810115695A CN 101293637 A CN101293637 A CN 101293637A
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Abstract
The invention discloses a device used for producing chlorine by hydrogen chloride in a way of catalytic oxidation and a method thereof. The invention is that a gas-solid countercurrent baffle is arranged in a fluidized bed reactor, thus leading a catalyst to be contacted with reactive gas in a way of countercurrent and then to react with the reactive gas so as to improve the ability of loading the chlorine, or by controlling operating temperature and installing a distribution plate, the fluidized bed reactor is divided into an oxidation section, an oxidation and chlorination section and a chlorination section, the three sections are connected together by a downstream tube and a riser tube outside the reactor, so as to realize the cyclic reaction and regeneration of the catalyst, the ability of loading the chlorine is improved after the catalyst reacts in an oxidation section, and the hydrogen chloride is transformed completely. The design not only avoids the catalysts and the reactive gas in the upper section and the lower section and the middle oxidation and chlorination section to be back-mixed in an axial direction, increases the use efficiency of the catalyst, and leads the hydrogen chloride of the raw material to realize complete conversion, but also increases the exit concentration of the chlorine. The used catalyst has good activity and the stability of the catalyst is increased greatly when being compared with ordinary oxychlorination catalysts. The reactor of the invention has the advantages of novel design, compact structure, being easy to be stably operated and controlled, high hydrogen chloride conversion rate and good hydrogen chloride selectivity, etc.
Description
Technical field
The present invention relates to a kind of device and processing method by producing chlorine gas with hydrogen chloride catalytic oxidation, and the catalyzer of realizing this method, chemical engineering process and equipment technical field belonged to.
Background technology
Chlorine is a kind of important and broad-spectrum Chemicals, it is the important source material of producing numerous chloride chemical, be mainly used in organic synthesis, as production plastics, synthetic rubber, synthon, dyestuff, agricultural chemicals, SYNTHETIC OPTICAL WHITNER, sterilizing agent, solvent etc., and other muriates.It mainly obtains by electrolytic saltwater in modern industry, and the by-product caustic soda forms so-called chlorine industry simultaneously.From global chlorine industry present situation, exist caustic soda excessive and contradiction that chlorine products is under-supply, i.e. chlor-alkali equilibrium problem.Because market need be improved the output of chlorine merely, a series of problems such as surplus that certainly will further aggravate caustic soda in continuous increase to chlorine by the development chlorine industry.Therefore, it is imperative to seek the source of newly arriving of chlorine.
As everyone knows, industrial many be the technological process by-product hydrogen chloride of raw material with chlorine.Along with the continuous development of chlorinated products industry, when chlorine demand increased day by day, the output of by-product hydrogen chloride also increased day by day, and the America and Europe is above 1,000 ten thousand tons.By-product hydrogen chloride corrodibility is strong and demand is little, and the neutralization discharging of superfluous by-product hydrogen chloride can cause environmental pollution, absorbs relieving haperacidity storage, transportation difficulty, and low price, is subject to the influence of various factorss such as market conditions.Therefore, be badly in need of finding a kind of economic and practical hydrogenchloride preparing chlorine gas technology, realize the closed cycle and the zero release of chlorine element.This both found a way out for by-product hydrogen chloride, had solved the chlor-alkali equilibrium problems that many areas exists again, therefore studied hydrogenchloride and prepared chlorine and have important industrial value and environment protection significance.Moreover, the successful exploitation of hydrogenchloride preparing chlorine gas technology also will produce decisive influence to many great chemical processes, form the industry of many novel procesies and high added value.
Report has a lot of hydrogenchloride to prepare the method for chlorine in document and the patent, mainly contain electrolytic process (Hine F, Noazki M., Kurata Y.Bench Scale Experiment of Recovery Chlorine from Waste Gas.J.Electrochem.Soc.1984,131,2834.), inorganic oxidizer direct oxidation method (van Dijk, C P, Schreiner W C.HydrogenChloride to Chlorine via the Kel-Chlor Process.Chem.Eng.Prog.1973,69,57.), catalytic oxidation (Deacon H, 1875, Improvements in manufacture of chlorine, US Patent165,802.).Electrolytic process has application example, and the direct oxidation method shortcoming is obvious, is difficult to realize the heavy industrialization application.As far back as 1876, Deacon proposed to load on the CuCl on inert support surface
2Make catalyzer, adopt catalytic oxidation by the hydrogenchloride preparing chlorine gas, its suitable temperature of reaction is 430～475 ℃, but because main reaction is an exothermic process, even if the HCl equilibrium conversion is also less than 85% under suitable reaction conditions, shortcoming such as poor catalyst stability and equipment is perishable in addition causes the Deacon process to fail to realize industrialization.In recent years, the foreign study person improves the Deacon process, released Shell process (FeurkeK H.Further Developments in the Shell Process for the Production of Chlorine byOxidation of Hydrogen Chloride.Chem Engr.1968,216,41.), MT-Chlor process (Furusaki, S.Catalytic Oxidation of Hydrogen Chloride in a Fluid Bed Reactor.AIChEJ.1973,19 (5): 1009-1016.) with Benson process (Minet R G, Tsotsis T T, Benson S W.Recovery ofchlorine from hydrogen chloride by carrier catalyst process.US Patent 4,994,256.) etc., wherein the Benson process is that oxi-chlorination is independently realized in the reactor at two, obtained certain producing effects, but owing to used two reactor polyphones, there are pressure reduction in oxychlorination and chlorination reactor, operation and control difficulty, instrument and cost of equipment are all higher, therefore, also there is the difficult problem that needs solve in the industrialization of this process.People (processing method of producing chlorine gas with hydrogen chloride catalytic oxidation and devices such as Korea Spro of Tsing-Hua University Framingham, Wei Fei, Chinese patent ZL02146784.6) on the basis of previous work, propose and studied two sections circulating fluid bed reactors, this technology and device make reactor have two close phases on axial height, needed the process of temperature distribution or concentration distribution to create condition, and owing to limited the gas axial backmixing, the gas reforming rate is significantly improved, and operability strengthens.But when in fact only setting two conversion zones, because the restriction of equilibrium conversion, the catalyzer composition is not enough to absorb fully unreacted residue hydrogen chloride gas in the oxychlorination section in the chlorination section, so the transformation efficiency of hydrogenchloride still can not satisfy the actual industrial needs.
Under above-mentioned disclosed situation, by catalyzer in the hydrogenchloride catalytic oxidation process oxychlorination and the polynary coupled microscopic mechanism of chlorination process in oxidation panel gas-solid counter flow oxidation, fluidized-bed reactor are studied, the result shows, the reason that hydrogenchloride can not transform fully is year chlorine scarce capacity of catalyzer in the chlorination section, cause to absorb fully the hydrogenchloride of oxychlorination Duan Zhongwei complete reaction, the content that is the cupric oxide in the chlorination section is not enough to absorb this part residue hydrogenchloride, makes that the conversion of hydrogenchloride is incomplete.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art part, a kind of device and method of new catalytic oxidation of hydrogen chloride for preparing chlorine gas is provided, make that it has the apparatus structure compactness, technical process is short, transformation efficiency is high.
Technical scheme of the present invention is as follows:
A kind of catalytic oxidation of hydrogen chloride for preparing is equipped with the device of chlorine, contain reactor body, HCI gas inlet 7, oxygen or gas inlet 9, riser tube 10, be arranged on the gas solid separation chamber 3 at reactor body top, and the gas distributor 8 that is arranged on the reactor body bottom, it is characterized in that: in described reactor body, be provided with the first gas-solid grid distributor 5, this gas-solid grid distributor is divided into two sections with reactor body, epimere is a chlorination section 4, hypomere is an oxychlorination section 6, and described HCI gas inlet is arranged on the middle part of oxychlorination section.
Technical characterictic of the present invention also is: be furnished with the solid adverse current baffle plate 11 of the wrong exhaust of multilayer in the oxychlorination section 6 on top, described HCI gas inlet, every layer of cap cone-shaped component by the perforate of a plurality of sides just arranged or wrong row forms.Percentage of open area at described cap cone-shaped component is 0～50%.
Another technical characterictic of the present invention is: be provided with downward-sloping deflector on the reactor wall face of oxychlorination section 6.
Second kind of technical scheme provided by the invention is:
A kind of catalytic oxidation of hydrogen chloride for preparing is equipped with the device of chlorine, it is characterized in that: be provided with the second gas-solid grid distributor 13 near the bottom, HCI gas inlet in the oxychlorination section, the oxychlorination section is divided into two sections, epimere is an oxychlorination section 6, hypomere is an oxidation panel 12, and at reactor body outer setting catalyzer down pipe 14, the two ends of this catalyzer down pipe are communicated with the top and the oxychlorination pars infrasegmentalis of chlorination section respectively.
In the technique scheme, the percentage of open area of the described first gas-solid grid distributor and the second gas-solid grid distributor is 3～50%.
The invention provides the method that a kind of catalytic oxidation of hydrogen chloride for preparing that adopts above-mentioned first kind of device is equipped with chlorine, it is characterized in that this method comprises the steps:
1) catalyzer is added reactor chlorination section from catalyst inlet 2,7 feed hydrogen chloride gas in the HCI gas inlet, and simultaneously at reactor bottom aerating oxygen or air, gas empty bed speed is between 0.2～0.8m/s, and the catalyst weight air speed is 0.1～3h
-1, the mol ratio of hydrogenchloride and oxygen is 1: 3～6: 1, described catalyzer comprises Primary Catalysts and promotor;
2) after the catalyst reactor particle flow is normal, begin reactor is heated, chlorination section temperature is 150～250 ℃, and oxychlorination section temperature is 350～450 ℃;
3) hydrogenchloride and oxygen also react the chlorine G﹠W that generates with the catalyzer counter current contact in oxychlorination section 6, product chlorine G﹠W and excess of oxygen and hydrogenchloride enter the chlorination section by gas-solid grid distributor 5, with the reacted catalyzer generation chlorination reaction that elevates from oxychlorination Duan Zhongjing catalyzer riser tube, absorb remaining hydrogenchloride, the catalyzer of saturated absorption hydrogenchloride enters the regeneration of oxychlorination section again, and the chlorine G﹠W and the excess of oxygen that generate in the chlorination section are discharged as product after gas solid separation.
The catalytic oxidation of hydrogen chloride for preparing that the invention provides the above-mentioned second kind of device of another kind of employing is equipped with the method for chlorine, it is characterized in that this method comprises the steps:
1) catalyzer is added reactor chlorination section from catalyst inlet 2,7 feed hydrogen chloride gas in the HCI gas inlet, and simultaneously at reactor bottom aerating oxygen or air, gas empty bed speed is between 0.2～0.8m/s, and the catalyst weight air speed is 0.1～3h
-1, the mol ratio of hydrogenchloride and oxygen is 1: 3～6: 1, described catalyzer comprises Primary Catalysts and promotor;
2) after the catalyst reactor particle flow is normal, begin reactor is heated, chlorination section temperature is 150～250 ℃, and oxychlorination section temperature is 350～450 ℃, 380～480 ℃ of oxidation panel temperature;
3) oxygen in oxidation panel 12 with catalyzer generation oxidizing reaction, generating portion chlorine, oxi-chlorination generation chlorine G﹠W takes place in the oxygen and the hydrogen chloride gas that come from oxidation panel the oxychlorination section, the hydrogenchloride of complete reaction and excess of oxygen do not enter in the chlorination section 4 through the first gas-solid grid distributor 5, the catalyzer of oxidized section lifting absorbs and makes hydrogenchloride transform fully, and the catalyzer behind the saturated absorption hydrogenchloride enters oxychlorination section 6 through down pipe; Product gas chlorine G﹠W and excess of oxygen enter gas solid separation chamber 3 with granules of catalyst separates, and solid particulate returns chlorination section 4, and gas and catalyzer are after further separating, and product gas flows out from reactor head.
Be equipped with in the method for chlorine one or more oxide compound or muriate among employed Primary Catalysts employing Cu, Cr, Fe, Mn and the Ni at catalytic oxidation of hydrogen chloride for preparing of the present invention.Employed promotor adopts the muriate of basic metal, alkaline-earth metal or ammonium, or the monohydric phosphate of basic metal, alkaline-earth metal or ammonium, dihydrogen phosphate or phosphoric acid salt.
The present invention is by being provided with the side perforate cap cone-shaped component that the multilayer different modes is arranged in the oxychlorination section, make the reaction of catalyzer and gas phase counter current contact, thereby the content of cupric oxide in the raising catalyzer after this part catalyzer is thus lifted to the chlorination section, is realized the absorption fully and the conversion of hydrogenchloride.In addition, set up an oxidation panel two sections bed bottoms, make catalyzer oxidation under excess oxygen earlier, change the wherein content of cupric oxide, and it is delivered to the chlorination section by riser tube, to improve in the chlorination section content of cupric oxide on the catalyzer, can make that incomplete hydrogenchloride fully absorbs in the oxychlorination section, thereby the maximum conversion rate of breaking hydrogenchloride in the single oxychlorination section is subjected to the restriction of equilibrium conversion, reaches hydrogenchloride 100% and transforms.Simultaneous oxidation section oxygen more than needed enters the oxychlorination section and continues reaction, and oxygen is rationally utilized.Because oxidizing reaction is an endothermic process, high temperature is favourable, and chlorination reaction is an exothermic process, and low temperature is favourable, and the oxychlorination process can make reaction be exothermic process oxidation and chlorination coupling, need not heat supply.Compared with prior art, technological process of the present invention has the following advantages and beneficial effect: 1. realize three different reaction process in a reactor, facility compact, short, quiet run and the control easily of technical process; 2. hydrogenchloride transformation efficiency height, selectivity are good, and transformation efficiency reaches 100%, and selectivity is greater than 99.5%; 3. the heat effect of reaction process coupling totally is heat release, and energy consumption is low; 4. catalyzer by modification after, active better, stability improves greatly, can satisfy industrial actual requirement.
Description of drawings
Fig. 1 is the structural representation of first kind of embodiment of the chlorination oxygen catalyzed oxidation provided by the invention device of producing chlorine.
Fig. 2 is the structural representation of another kind of embodiment of the device of producing chlorine gas with hydrogen chloride catalytic oxidation provided by the invention.
Fig. 3 is the structural representation of a cap cone-shaped component in every layer of gas-solid adverse current baffle plate.
Fig. 4 is that the cap cone-shaped component is arranged synoptic diagram every layer mistake.
Wherein: 1, pneumatic outlet; 2, catalyst inlet; 3, gas solid separation chamber; 4, chlorination section; 5, the first gas-solid grid distributor; 6, oxychlorination section; 7, hydrogenchloride inlet; 8, gas distributor; 9, oxygen or gas inlet; 10, riser tube; 11, gas-solid adverse current baffle plate; 12, oxidation panel; 13, the second gas-solid grid distributor; 14, catalyzer down pipe; 15, cap cone-shaped component.
Embodiment
Below in conjunction with accompanying drawing, principle of the present invention, structure and technical process embodiment are further specified:
In reaction unit as shown in Figure 1, the first gas-solid grid distributor 5 is set, the fluidized-bed reactor main body is divided into two sections, epimere is a chlorination section 4, hypomere is an oxychlorination section 6, just can form two emulsion zones in fluidized-bed reactor inside like this, and, realize the circulating reaction and the regeneration of catalyzer at fluidized-bed reactor outer setting riser tube 10.Set up the solid adverse current baffle plate 11 of the wrong exhaust of multilayer at oxychlorination section 6 internal upper parts of two sections circulating fluid bed reactors, every layer of cap cone-shaped component 15 by the perforate of a plurality of sides just arranged or wrong row forms.The percentage of open area of cap cone-shaped component is 0～50%.Also can on the reactor wall face of oxychlorination section 6, be provided with downward-sloping deflector.Catalyzer is from top to bottom along the 15 outside surface landings of cap cone-shaped component, reactant gases also reacts with the catalyzer counter current contact from inside to outside through the cap tapered hole, the ratio content longshore current fluidized bed reactor of cupric oxide axially improves downwards gradually in the catalyzer, catalyzer is again after riser tube 10 is sent into reactor chlorination section 4, absorb in the oxychlorination section 6 the not hydrogenchloride of complete reaction, make it to transform fully.
Catalyzer joins the fluidized-bed reactor body interior from catalyst inlet 2, can all enter reactor in order to make catalyzer, can be at oxygen or gas inlet 9 aerating oxygens or the air of reactor bottom when adding catalyzer.When oxygen or air capacity hour, most of granules of catalyst rests on reactor bottom, along with gas speed increases, granules of catalyst makes progress gradually, close phase descends highly gradually in the oxychlorination section 6, close phase increases highly gradually in the chlorination section 4.Along with gas speed continues to increase, the particle in the oxychlorination section may be blown sky fully, and this belongs to upset operation, desire the normal running of realization response device, the percentage of open area of the first gas-solid grid distributor and the second gas-solid grid distributor should be preferably 5～15% 3～50%, and corresponding gas speed is between 0.2～0.8m/s.After granules of catalyst in the fluidized-bed reactor flows normally, begin reactor is heated, when the temperature of chlorination section 4 surpasses 250 ℃, open cooling water system.When oxychlorination section 6 temperature are 350～450 ℃, when chlorination section temperature is 150～250 ℃, feed hydrogen chloride gas, and increase gradually hydrogenchloride amount, reduce the amount of oxygen or air, making the mol ratio of hydrogenchloride and oxygen is 1: 3～6: 1, is preferably 1: 2～4: 1, reduces simultaneously to add heat, increase the amount of water coolant, reach set(ting)value until temperature of reaction.
Hydrogenchloride and oxygen also react with the catalyzer counter current contact in oxychlorination section 6, and the content of cupric oxide increases downwards one by one in the catalyzer, enter in the chlorination section through the catalyzer riser tube again.Chlorine, water and excess of oxygen and hydrogenchloride that the reaction of oxychlorination section generates enter the chlorination section by gas-solid grid distributor 5, the catalyzer that elevates with the oxychlorination section contacts, chlorination reaction takes place under lower temperature, absorb remaining hydrogenchloride, the catalyzer of saturated absorption hydrogenchloride returns the regeneration of oxychlorination section, and the chlorine, water and the excess of oxygen that generate in the section of chlorination are simultaneously discharged as product after gas solid separation.
In fluidized-bed reactor as shown in Figure 2, form two sections circulating fluid bed reactors by the riser tube 10 that the first gas-solid grid distributor 5 and reactor outside are set, in the oxychlorination section 6 of two sections circulating fluid bed reactors, be provided with the second gas-solid grid distributor 13 again near the bottom, HCI gas inlet, the oxychlorination section is divided into two sections, epimere is an oxychlorination section 6, hypomere is an oxidation panel 12, and at reactor body outer setting catalyzer down pipe 14, the two ends of this catalyzer down pipe are communicated with the top and the oxychlorination pars infrasegmentalis of chlorination section respectively.Cupric oxide content is purpose in the catalyzer to improve purely in oxidation panel, catalyzer and oxygen are reacted separately, reacted catalyzer enters the hydrogenchloride of chlorination section with absorption oxychlorination Duan Zhongwei complete reaction through the catalyzer riser tube again, thereby realizes the conversion fully of hydrogenchloride.
Adopt preceding method, make behind the catalyzer stabilization fluid of each section, begin reactor is heated, chlorination section temperature is 150～250 ℃, and oxychlorination section temperature is 350～450 ℃, 380～480 ℃ of oxidation panel temperature.7 feed hydrogen chloride gas from the HCI gas inlet, and simultaneously at reactor bottom aerating oxygen or air, gas empty bed speed is between 0.2～0.8m/s, and the catalyst weight air speed is 0.1～3h
-1, the mol ratio of hydrogenchloride and oxygen is 1: 3～6: 1, oxygen in oxidation panel 12 with catalyzer generation oxidizing reaction, the content of cupric oxide improves in the generating portion chlorine, this moment catalyzer, and enters in the chlorination section 4 by the catalyzer riser tube.In oxychlorination section 6, the oxygen and the hydrogenchloride generation oxi-chlorination that come from oxidation panel 12 generate the chlorine G﹠W, the hydrogenchloride of complete reaction and excess of oxygen do not enter in the chlorination section 4 through the first gas-solid grid distributor 5, in the chlorination section 4 main chlorination reactions that take place, be that the catalyzer that oxidation panel 12 promotes absorbs the not hydrogenchloride of complete reaction, make hydrogenchloride transform fully, catalyzer behind the saturated absorption hydrogenchloride enters in the oxychlorination section 6 through down pipe 14, product gas chlorine G﹠W and excess of oxygen and granules of catalyst enter gas solid separation chamber 3 and carry out gas solid separation, solid particulate is because chlorination section 4 is returned in the effect of gravity, product gas and catalyzer are after further separating, product gas flows out from reactor head, and solid particulate then returns chlorination section 4.
Employed Primary Catalysts adopts among Cu, Cr, Fe, Mn and the Ni one or more oxide compound or muriate in the inventive method; Employed promotor adopts the muriate of basic metal, alkaline-earth metal or ammonium, or the dibasic phosphate of basic metal, alkaline-earth metal or ammonium, dihydrogen phosphate or phosphoric acid salt.
The product gas that fluidized-bed reactor comes out, at first pass through water wash column, with the granules of catalyst that the dilute hydrochloric acid washing is taken out of, the gas after the washing enters drying tower (absorbing moisture as the available vitriol oil), sloughs moisture content wherein, obtain the chlorine of butt and the gas mixture of oxygen, separated by chlorine oxygen tripping device again, after the compressed machine compression of chlorine, obtain the product liquid chlorine, the oxygen of separating, but Returning reactor continues to participate in reaction.If use industrial oxygen, may contain more rare gas element composition, need be the gas emptying behind certain interval of time.
Embodiment
Below be apparatus of the present invention can range of application prepare the non-limiting example in chlorine (or in related application field) by hydrogenchloride.These embodiment have further described and have illustrated the embodiment in the scope of the invention.The embodiment that provides only is used for illustrative purposes, and the present invention is not constituted any qualification, can carry out various changes to it under the condition that does not deviate from spirit and scope of the invention, all is that those of ordinary skills approve.
React in reactor as shown in Figure 1, raw material is pure hydrogenchloride and oxygen, and its raw materials components mole ratio is 1: 3, and the oxychlorination temperature is 450 ℃, and chlorination section temperature is 150 ℃, and working pressure is 0.11MPa, and the hydrogenchloride mass space velocity is 0.8h
-1, the transformation efficiency that obtains hydrogenchloride is 100%, and oxygen conversion is 8.3%, and wherein the contents on dry basis of chlorine is 13.3% in the product.
React in reactor as shown in Figure 1, raw material is pure hydrogenchloride and oxygen, and its raw materials components mole ratio is 6: 1, and the oxychlorination temperature is 350 ℃, and chlorination section temperature is 250 ℃, and working pressure is 0.11MPa, and the hydrogenchloride mass space velocity is 0.1h
-1, the transformation efficiency that obtains hydrogenchloride is 50%, and oxygen conversion is 75%, and wherein the contents on dry basis of chlorine is 24% in the product.
React in reactor as shown in Figure 1, raw material is pure hydrogenchloride and oxygen, and its raw materials components mole ratio is 4: 1, and the oxychlorination temperature is 450 ℃, and chlorination section temperature is 200 ℃, and working pressure is 0.11MPa, and the hydrogenchloride mass space velocity is 0.45h
-1, the transformation efficiency that obtains hydrogenchloride is 98%, and oxygen conversion is 98%, and wherein the contents on dry basis of chlorine is 99% in the product.
In three sections circulating fluid bed reactors as shown in Figure 2, react.Raw material is pure hydrogenchloride and oxygen, and its raw materials components mole ratio is 1: 3, and the oxidation panel temperature is 480 ℃, and oxychlorination section temperature is 400 ℃, and the chlorination section is 250 ℃, and working pressure 0.11MPa, the mass space velocity of hydrogenchloride are 0.7h
-1, the transformation efficiency that obtains hydrogenchloride is 99%, and oxygen conversion is 8%, and outlet chlorine butt mass content is 13%.
Feed hydrogenchloride and oxygen at three sections circulating fluid bed reactor different material inlets, its mol ratio is 4: 4.4, and the temperature of oxidation panel and oxychlorination section is 450 ℃, and the chlorination section is 150 ℃, and working pressure 0.11MPa, the mass space velocity of hydrogenchloride are 3h
-1, obtaining the hydrogenchloride transformation efficiency is 98%, and oxygen conversion is 22.3%, and outlet chlorine contents on dry basis is 35.9%.
Feed hydrogenchloride and oxygen at three sections circulating fluid bed reactor different material inlets, its mol ratio is 4: 1.5,480 ℃ of oxidation panel temperature, and oxychlorination section temperature is 400 ℃, and the chlorination section is 200 ℃, and working pressure 0.11MPa, the mass space velocity of hydrogenchloride are 0.45h
-1, obtaining the hydrogenchloride transformation efficiency is 99.5%, and oxygen conversion is 66.3%, and outlet chlorine contents on dry basis is 79.1%.
Feed hydrogenchloride and oxygen at three sections circulating fluid bed reactor different material inlets, its mol ratio is 1: 6, and the temperature of oxidation panel and oxychlorination section is 450 ℃, and the chlorination section is 200 ℃, and working pressure 0.11MPa, the mass space velocity of hydrogenchloride are 0.1h
-1, obtaining the hydrogenchloride transformation efficiency is 50%, and oxygen conversion is 75%, and outlet chlorine contents on dry basis is 24%.
Feed hydrogenchloride and air at three sections circulating fluid bed reactor different material inlets, its mol ratio is 1: 2, and the temperature of oxidation panel and oxychlorination section is 450 ℃, and the chlorination section is 200 ℃, and working pressure 0.11MPa, the mass space velocity of hydrogenchloride are 0.8h
-1, obtaining the hydrogenchloride transformation efficiency is 97%, and oxygen conversion is 60.6%, and outlet chlorine contents on dry basis is 21.3%.
Claims (10)
1. a catalytic oxidation of hydrogen chloride for preparing is equipped with the device of chlorine, contain the fluidized-bed reactor main body, HCI gas inlet (7), oxygen or gas inlet (9), riser tube (10), be arranged on the gas solid separation chamber (3) at reactor body top, and the gas distributor (8) that is arranged on the reactor body bottom, it is characterized in that: in described reactor body, be provided with the first gas-solid grid distributor (5), this gas-solid grid distributor is divided into two sections with the fluidized-bed reactor main body, epimere is chlorination section (4), hypomere is oxychlorination section (6), and described HCI gas inlet is arranged on the middle part of oxychlorination section.
2. the device that is equipped with chlorine according to the described a kind of catalytic oxidation of hydrogen chloride for preparing of claim 1, it is characterized in that: be furnished with the solid adverse current baffle plate (11) of the wrong exhaust of multilayer in the oxychlorination section (6) on top, described HCI gas inlet, every layer of cap cone-shaped component by the perforate of a plurality of sides just arranged or wrong row forms.
3. be equipped with the device of chlorine according to the described a kind of catalytic oxidation of hydrogen chloride for preparing of claim 2, it is characterized in that: on the reactor wall face of oxychlorination section (6), be provided with downward-sloping deflector.
4. be equipped with the device of chlorine according to the described a kind of catalytic oxidation of hydrogen chloride for preparing of claim 2, it is characterized in that: the percentage of open area at described cap cone-shaped component is 0～50%.
5. the device that is equipped with chlorine according to the described a kind of catalytic oxidation of hydrogen chloride for preparing of claim 1, it is characterized in that: be provided with the second gas-solid grid distributor (13) near the bottom, HCI gas inlet in the oxychlorination section, the oxychlorination section is divided into two sections, epimere is oxychlorination section (6), hypomere is oxidation panel (12), and at reactor body outer setting catalyzer down pipe (14), the two ends of this catalyzer down pipe are communicated with the top and the oxychlorination pars infrasegmentalis of chlorination section respectively.
6. be equipped with the device of chlorine according to claim 1 or 5 described a kind of catalytic oxidation of hydrogen chloride for preparing, it is characterized in that: the percentage of open area of the described first gas-solid grid distributor and the second gas-solid grid distributor is 3～50%.
7. an employing is equipped with the method for chlorine as the catalytic oxidation of hydrogen chloride for preparing of device as described in the claim 1,2 or 3, it is characterized in that this method comprises the steps:
1) catalyzer is added reactor chlorination section from catalyst inlet (2), (7) feed hydrogen chloride gas in the HCI gas inlet, and simultaneously at reactor bottom aerating oxygen or air, gas empty bed speed is between 0.2～0.8m/s, and the catalyst weight air speed is 0.1～3h
-1, the mol ratio of hydrogenchloride and oxygen is 1: 3～6: 1, described catalyzer comprises Primary Catalysts and promotor;
2) after the catalyst reactor particle flow is normal, begin reactor is heated, chlorination section temperature is 150～250 ℃, and oxychlorination section temperature is 350～450 ℃;
3) hydrogenchloride and oxygen also react the chlorine G﹠W that generates with the catalyzer counter current contact in oxychlorination section (6), product chlorine G﹠W and excess of oxygen and hydrogenchloride enter the chlorination section by gas-solid grid distributor (5), with the reacted catalyzer generation chlorination reaction that elevates from oxychlorination Duan Zhongjing catalyzer riser tube, absorb remaining hydrogenchloride, the catalyzer of saturated absorption hydrogenchloride enters the regeneration of oxychlorination section again, and the chlorine G﹠W and the excess of oxygen that generate in the chlorination section are discharged as product after gas solid separation.
8. an employing is equipped with the method for chlorine as the catalytic oxidation of hydrogen chloride for preparing of device as described in the claim 5, it is characterized in that this method comprises the steps:
1) catalyzer is added reactor chlorination section from catalyst inlet (2), (7) feed hydrogen chloride gas in the HCI gas inlet, and simultaneously at reactor bottom aerating oxygen or air, gas empty bed speed is between 0.2～0.8m/s, and the catalyst weight air speed is 0.1～3h
-1, the mol ratio of hydrogenchloride and oxygen is 1: 3～6: 1, described catalyzer comprises Primary Catalysts and promotor;
2) after the catalyst reactor particle flow is normal, begin reactor is heated, chlorination section temperature is 150～250 ℃, and oxychlorination section temperature is 350～450 ℃, 380～480 ℃ of oxidation panel temperature;
3) oxygen in oxidation panel (12) with catalyzer generation oxidizing reaction, generating portion chlorine, oxi-chlorination generation chlorine G﹠W takes place in the oxygen and the hydrogen chloride gas that come from oxidation panel the oxychlorination section, the hydrogenchloride of complete reaction and excess of oxygen do not enter in the chlorination section (4) through the first gas-solid grid distributor (5), the catalyzer of oxidized section lifting absorbs and makes hydrogenchloride transform fully, and the catalyzer behind the saturated absorption hydrogenchloride enters oxychlorination section (6) through down pipe; Product gas chlorine G﹠W and excess of oxygen enter gas solid separation chamber (3) with granules of catalyst separates, and solid particulate returns chlorination section (4), and gas and catalyzer are after further separating, and product gas flows out from reactor head.
9. be equipped with the method for chlorine according to claim 7 or 8 described catalytic oxidation of hydrogen chloride for preparing, it is characterized in that: employed Primary Catalysts adopts among Cu, Cr, Fe, Mn and the Ni one or more oxide compound or muriate.
10. catalytic oxidation of hydrogen chloride for preparing according to claim 9 is equipped with the method for chlorine, it is characterized in that: employed promotor adopts the muriate of basic metal, alkaline-earth metal or ammonium, or the dibasic phosphate of basic metal, alkaline-earth metal or ammonium, dihydrogen phosphate or phosphoric acid salt.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102459068A (en) * | 2009-06-24 | 2012-05-16 | 巴斯夫欧洲公司 | Method for producing chlorine from hcl |
| KR20160030456A (en) * | 2014-09-10 | 2016-03-18 | 아이에프피 에너지스 누벨 | Regenerator for catalysts |
| KR20160030455A (en) * | 2014-09-10 | 2016-03-18 | 아이에프피 에너지스 누벨 | Regenerator for regenerating catalysts under different operating conditions |
| CN105502293A (en) * | 2016-01-25 | 2016-04-20 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Method for preparing chlorine through low-temperature plasma |
| CN106082130A (en) * | 2016-08-12 | 2016-11-09 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | A kind of method that plasma method hydrochloric acid prepares chlorine |
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| JP2595018B2 (en) * | 1988-03-01 | 1997-03-26 | 三井東圧化学株式会社 | Method for producing chlorine |
| CN1188342C (en) * | 2002-11-08 | 2005-02-09 | 巨化集团公司 | Technological process and equipment for catalytically oxidizing HCl to produce CL2 |
| DE102004006610A1 (en) * | 2004-02-11 | 2005-09-01 | Basf Ag | Reactor and process for producing chlorine from HCl |
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| KR20160030455A (en) * | 2014-09-10 | 2016-03-18 | 아이에프피 에너지스 누벨 | Regenerator for regenerating catalysts under different operating conditions |
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| CN106082130A (en) * | 2016-08-12 | 2016-11-09 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | A kind of method that plasma method hydrochloric acid prepares chlorine |
| CN106335878A (en) * | 2016-08-12 | 2017-01-18 | 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) | Method for preparing chlorine gas from hydrochloric acid |
| US11369934B2 (en) | 2019-09-24 | 2022-06-28 | Lg Chem, Ltd. | Fluidized bed reactor |
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