CN1900036A - Fluidized bed reactor for preparing vinyl chloride by hydrogen chloride and acetylene reaction and method - Google Patents
Fluidized bed reactor for preparing vinyl chloride by hydrogen chloride and acetylene reaction and method Download PDFInfo
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- CN1900036A CN1900036A CN 200610089622 CN200610089622A CN1900036A CN 1900036 A CN1900036 A CN 1900036A CN 200610089622 CN200610089622 CN 200610089622 CN 200610089622 A CN200610089622 A CN 200610089622A CN 1900036 A CN1900036 A CN 1900036A
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Abstract
The fluidized bed reactor for preparing vinyl chloride through reaction between hydrogen chloride and acetylene and preparation process belongs to the field of chemical technology. The fluidized bed reactor includes fluidized bed, reactant material gas inlet, heat exchange pipes, member, cyclonic separator, reacted gas outlet, catalyst feeding port and catalyst removing port connected successively to the wall of the fluidized bed. After the catalyst in the molar ratio to the reactant material of 1.01-1.1 to 1 is fed, hydrogen chloride and acetylene are introduced are converted through reaction into vinyl chloride completely, and the reacted product is made to enter the post equipment through the gas outlet. The present invention has simple reaction member, high bubble crushing effect, low catalyst loss, greatly strengthened gas-solid contact, high vinyl chloride product purity and other advantages.
Description
Technical field
The present invention relates to a kind ofly prepare the fluidized bed reactor equipment and the processing method of vinylchlorid, belong to chemical engineering process and equipment technical field by hydrogenchloride and acetylene reaction.
Background technology
Vinylchlorid is the monomer of preparation polyvinyl chloride, is the very important chemical intermediate of a class.Along with the widespread use of pvc material in fields such as wrapping material, the output of vinylchlorid and polyvinyl chloride improves rapidly, and the annual requirement of China is about 800-1000 is ten thousand tons.
The method of suitability for industrialized production vinylchlorid has three kinds at present, promptly prepares vinylchlorid with hcl reaction respectively by acetylene, ethene or ethane.The source of ethene is mainly petroleum refining industry, because crude oil price rises rapidly, causes the price of ethene to rise in recent years, though its technology of preparing maturation, production cost can be in any more.The source of ethane is natural gas field, is subjected to the region restricted strong.And acetylene can be obtained by calcium carbide (being got by the compound of coal and calcium) hydrolysis.Owing to rich coal resources, the acetylene preparation cost is relatively low, so prepare vinylchlorid in China by acetylene method the bigger market space is arranged in China.
The principle that acetylene method prepares vinylchlorid is that hydrogenchloride and acetylene are heated to about 100 ℃, feeds reactor, under the effect of load type metal chloride catalyst, generates vinylchlorid down at 100-180 ℃.
The key of this process is that requirement acetylene will be transformed as far as possible, and the purity of vinylchlorid could improve like this, and the acetylene of postorder reclaims load and alleviates.Carry out above-mentioned reaction at the industrial fixed-bed reactor that often utilize and since fixed bed in particle size greater than 3 millimeters, under this thermopositive reaction, the temperature of granule interior often is higher than the body gas temperature.The exchange capability of heat of fixed bed is low simultaneously, often causes focus to produce.Be lower than 20% metal chloride owing to contain in the catalyzer, and the metal chloride boiling point is low, easily distillation, above-mentioned two characteristics are unfavorable for the thermostability that keeps catalyzer, thus the air speed that actual catalyzer can bear is lower.Simultaneously, catalyzer is tight in the fixed bed, and the bed pressure drop height can not be with the operation of high gas speed, and this shortcoming makes the throughput of separate unit fixed bed be subjected to severely restricts.
In order to change above-mentioned shortcoming, once there was the method for fluidisation bench grafting fixed bed to prepare vinylchlorid.Utilize on the one hand in the fluidized-bed particle little, catalyst activity height, heat transfer coefficient height easily make the uniform characteristics of temperature, make that acetylene is most of to be transformed.Utilize fixed-bed reactor that the transformation efficiency of acetylene is improved on the other hand again.But in this technology, because the gas speed of process or the restriction that pressure drop still is subjected to fixed bed, its production intensity is still not as good as single fluidized-bed.Simultaneously, in that fluidized bed gas sparger distribution effect was relatively poor at that time, component technology is immature, fluidized-bed amplifying technique imperfection, and the conversion of alkyne in fluidized-bed only reaches about 74%, and the load of the fixed bed that connects after making is heavier.While said structure more complicated, the coordination control of the two acquires a certain degree of difficulty.
Summary of the invention
The reactor production intensity is crossed deficiency low and that temperature control is bad when the objective of the invention is at the prepared vinylchlorid of prior art, provide a kind of fluidized-bed that adopts new and effective gas distributor and member to carry out device and processing method that hydrogenchloride and acetylene reaction prepare vinylchlorid, in a fluidized-bed reactor, reach the purpose of efficient conversion acetylene.Have reactor production intensity height, turndown ratio is big, the conversion of alkyne height, and the selectivity height of generation vinylchlorid, catalyst levels is few, and catalyst life is long, less investment, low power consumption and other advantages.
Technical scheme of the present invention is as follows:
1. hydrogenchloride and acetylene reaction prepare the fluidized-bed reactor of vinylchlorid, it is characterized in that this reactor comprises:
(a) fluidized-bed (1);
(b) one is arranged on the reaction raw materials gas inlet (2) of fluidized-bed (1) bottom and the gas distributor (3) that is arranged on this inlet top;
(c) one or more heat transfer tubes (5) that are arranged on gas distributor (3).Heat transfer tube (5) links to each other with the barrel of fluidized-bed (1);
(d) one or more members (6) that are fixed on the heat transfer tube (5);
(e) one or more groups is arranged on fluidized-bed top, is used for the cyclonic separator (8) of catalyst recovery, and cyclonic separator (8) is fixed on the barrel on fluidized-bed (1) top;
(f) reaction gas outlet (9) that is arranged on fluidized-bed top, this outlet links to each other with cyclonic separator (8);
(g) catalyzer that is arranged on the fluidized-bed middle part adds inlet (7), and this adds inlet and links to each other with the barrel of fluidized-bed (1);
(h) the shifting out an of spent catalyst that is arranged on fluidized-bed bottom mouthful (4), this barrel that shifts out mouthful bottom fluidized-bed (1) links to each other.
In order to make the efficient conversion of hydrogenchloride and acetylene, the present invention can use the gas distributor of high pressure drop to carry out the gas initial distribution, controls its fluidized.The pressure drop of sparger is the 20%-35% of beds total pressure drop, and the ratio that diameter is not more than the bubble of 4mm in the incipient bubble that is produced by sparger is 75%-90% like this.The form of gas distributor comprises variable mass drift tube type sparger, multiaperture-type sparger, float-valve type sparger.
In order to make the fluidized-bed bottom temp be no more than the fusing point of volatile substances on the catalyzer and the selectivity that assurance generates vinylchlorid, the bottom of heat transfer tube can not be too big apart from the distance of gas distributor among the present invention, between 50-300mm.For a large amount of reaction heat is effectively shifted out, the sufficient heat interchanging area of the present invention, the height of heat transfer tube are the 100%-200% of catalyzer emulsion zone static height simultaneously, and the sectional area of heat transfer tube accounts for the 5%-30% of fluidized-bed sectional area.
Simultaneously, in order to guarantee sufficient fluidization effect, by control acetylene air speed and the loadings of catalyzer and the charge ratio of hydrogenchloride and acetylene, the gas speed in the may command fluidisation bed is at 0.1-0.9m/s.In order to guarantee the wearing and tearing of conversion of alkyne and minimizing catalyzer, the present invention can use particle diameter to be 0.05-0.5mm simultaneously, and specific surface area is 600-1200m
2/ g, tap density is 300-1000kg/m
3, intensity is greater than the muriatic catalyzer of the containing metal of 70% (ball milled).
In order to suppress the coalescence trend of bubble at uphill process, increase the gas-solid contact efficiency, improve the transformation efficiency of acetylene.The present invention can use a large amount of member bubble crushing.The member of horizontal positioned is fixed on the heat transfer tube, and its porosity is 50%-90%.Simultaneously for effectively, bubble crushing constantly, two-layer member cross arrangement that can be adjacent among the present invention, intersecting angle is 45 °-90 °.Height between two-layer member is the 20%-100% of fluidized-bed diameter.With the distance between layer member is the 1%-20% of fluidized-bed diameter.
Overflow for fear of catalyzer, contaminate subsequent system and lose catalyst activity, and guarantee suitable pressure drop, using gas cyclonic separator of the present invention carries out catalyst recovery.
Simultaneously, the method that provides a kind of hydrogenchloride and acetylene reaction to prepare vinylchlorid, this method comprises the steps:
(1) member (6) is fixed on the heat transfer tube (5), inlet (2), gas distributor (3), catalyst outlet (4), heat transfer tube (5), catalyst inlet (7), the cyclonic separator (8) of gas are linked to each other with the barrel of fluidized-bed (1) successively with pneumatic outlet (9), and formation has complete fluidized-bed (1) reactor;
(2) use particle diameter to be 0.05-0.5mm, specific surface area is 600-1200m
2/ g, tap density is 300-1000kg/m
3, intensity is greater than the muriatic catalyzer of the containing metal of 70% (ball milled), and metal chloride is the muriate of mercury, the muriate of tin, the muriate of copper, the muriate of zinc, the muriate of manganese, the muriate of lanthanum.Catalyzer is entered fluidized-bed (1) from catalyst inlet (7).In order to make catalyzer not stop up gas distributor (3), feed nitrogen or air by fluidized-bed gas inlet, bottom (2) through gas distributor (3) when adding catalyzer.Down loosening at less nitrogen of flow or air, granules of catalyst enters fluidized-bed from catalyst inlet 7, is deposited in the zone of gas distributor (3) top in the fluidized-bed (1).The static loading height of catalyzer is 3-10 a times of fluidized-bed diameter.
(3) catalyzer is all packed into behind the fluidized-bed (1), make the catalyzer in the fluidized-bed (1) be in fluidized state by the logical rare gas element (nitrogen) of gas feed (2).Feeding high temperature heat transferring medium in heat transfer tube (5) (high-temperature water, high-temperature steam, high temperature inert gas or high temperature oil, temperature is greater than 120 ℃), make the temperature in the fluidized-bed (1) be increased to 100-120 ℃ gradually.
(4) fed the gas mixture of hydrogenchloride and acetylene by gas inlet (2) and sparger (3) in fluidized-bed (1), control hydrogenchloride is 1.01 with the mol ratio of acetylene: 1-1.1: 1, and the interior volume space velocity of fluidized-bed is 20～200Nm
3Acetylene/m3 catalyzer/hour (economize slightly hour
-1).Heat is emitted in reaction, and temperature is increased to 110-175 ℃ gradually in the fluidized-bed (1).
(5) heating medium with heat transfer tube (5) switches to heat-eliminating medium, and heat-eliminating medium is the lower water of temperature, gas, and oil, the temperature in the place (hereinafter to be referred as the catalyzer emulsion zone) of (1) catalyst buildup is between 110～175 ℃ in the control fluidized-bed.
(6) behind acetylene and the hydrogenchloride process catalyzer emulsion zone, almost be converted into vinylchlorid fully.A spot of acetylene and hydrogenchloride and a large amount of vinylchlorid gas, process cyclonic separator (8) goes out fluidized-bed from the pneumatic outlet (9) of fluidized-bed, enters follow-up tripping device.
(7) the part catalyzer in the catalyzer emulsion zone is carried by air-flow, enters cyclonic separator (8), and the bottom of process cyclonic separator (8) is back to the catalyzer emulsion zone.
(8) behind catalyst deactivation, discharge from the outlet (4) of fluidized-bed (1) bottom.Add catalyzer from catalyst inlet (7) to fluidized-bed (1) simultaneously, the assurance process is moved continuously.
Hydrogenchloride provided by the invention and acetylene reaction prepare the fluidized-bed of vinylchlorid, adopted the better sparger of gas distribution effect, less to catalyst abrasion rate (voidage is bigger), the member that but has good bubble crushing, and activity is higher and the reliable more catalyzer of intensity, make the gas-solid contact effect in the fluidized-bed strengthen greatly, promoted the conversion of acetylene.The heat transfer tube that is provided with in fluidized-bed has simultaneously guaranteed in time shifting out of reaction heat, makes in the fluidized-bed temperature lower and even, has suppressed the excessive addition reaction (generation ethylene dichloride) of acetylene, has improved the selectivity that generates vinylchlorid.Simultaneously, make follow-up gas delivery burden alleviate the vinylchlorid product purity height of generation.
And the present invention is compared with prior art, has the following advantages and beneficial effect:
(1) compares with the large granular catalyst (diameter is 3-5mm) that uses in the present fixed bed, catalyzer of the present invention is that mean diameter only is the catalyst particle of 0.05-0.5mm, there is not the granule interior overheating problem, the metal chloride component that can suppress on the catalyzer runs off, and life of catalyst can be increased to 2-3 times of catalyzer in the fixed bed.Substantially there is not the hole inside diffusional resistance owing to short grained catalyzer simultaneously, the catalyst activity height, catalyzer is effective with contacting of reaction gas.Guaranteeing the acetylene air speed can be increased to 3-5 times of acetylene air speed in the fixed bed under the constant prerequisite of conversion of alkyne.
(2) compare with traditional fixed-bed reactor, when reaching changing effect identical with fixed bed and throughput, use fluidized-bed of the present invention and technology can significantly reduce catalyst levels, save the about 50%-100% of catalyzer, investment cost is few.
(3) fluidized-bed among the present invention is than the high 500-1000 of heat-transfer capability times of fixed-bed reactor, and under the prerequisite of identical heat interchanging area, the throughput of reactor section of the present invention improves 30%-300% than fixed bed.Guaranteeing to reduce the number of reactor significantly under the constant prerequisite of overall manufacturing, operation instrument and regulate expenditure have been reduced.
(4) compare with existing fluidisation bench grafting fixed-bed process, the pressure drop height of the sparger in the fluidized-bed among the present invention, gas distribution is effective.Member is simple simultaneously, bubble crushing is effective, the catalyst abrasion rate is low.Fluidized bed process is steady, controls easy.
(5) compare with fixed-bed process, the inactivation fine powder catalyst of fluidized-bed is changed convenient, can be delivered at short notice in the tightness system, saves manually, is beneficial to environmental protection.
Description of drawings
Fig. 1 is a fluidized-bed reactor structural representation of the present invention.Wherein, 1. fluidized-bed; 2. gas enters the inlet of fluidized-bed; 3. gas distributor; 4. decaying catalyst draws off the outlet of fluidized-bed; 5. heat transfer tube; 6. member; 7. catalyzer enters the inlet of fluidized-bed; 8. the inlet of cyclonic separator; 9. gas goes out the outlet of fluidized-bed.
Embodiment
Below in conjunction with accompanying drawing 1 and embodiment reactor of the present invention and method are described.
Fig. 1 prepares the structural representation of the fluidized-bed reactor of vinylchlorid for acetylene of the present invention and hcl reaction.Among the figure: 1. fluidized-bed; 2. gas enters the inlet of fluidized-bed; 3. gas distributor; 4. decaying catalyst draws off the outlet of fluidized-bed; 5. heat transfer tube; 6 members.; 7. catalyzer enters the inlet of fluidized-bed; 8. the inlet of cyclonic separator; 9. gas goes out the outlet of fluidized-bed.Member (6) is fixed on the heat transfer tube (5), inlet (2), gas distributor (3), catalyst outlet (4), heat transfer tube (5), catalyst inlet (7), the cyclonic separator (8) of gas are linked to each other with the barrel of fluidized-bed (1) successively with pneumatic outlet (9), and formation has complete fluidized-bed (1).Catalyzer enters fluidized-bed (1) from catalyst inlet (7).In order to make catalyzer not stop up gas distributor (3), feed nitrogen or air by fluidized-bed gas inlet, bottom (2) through gas distributor (3) when adding catalyzer.Down loosening at less nitrogen of flow or air, granules of catalyst enters fluidized-bed from catalyst inlet 7, is deposited in the zone of gas distributor (3) top in the fluidized-bed (1).Catalyzer is all packed into behind the fluidized-bed (1), make the catalyzer in the fluidized-bed (1) be in fluidized state by the logical rare gas element of gas feed (2).Feeding high temperature heat transferring medium in heat transfer tube (5) (high-temperature water, high-temperature steam, high temperature inert gas or high temperature oil, temperature is greater than 120 ℃), make the temperature in the fluidized-bed (1) be increased to 100-120 ℃ gradually.Feed hydrogenchloride and acetylene by gas inlet (2) gradually through gas distributor (3) then.Heat is emitted in reaction, and temperature is increased to 110-175 ℃ gradually in the fluidized-bed (1).In this process the heat transferring medium in the heat transfer tube 6 is switched to heat-eliminating medium (water at low temperature, cryogenic gas or low temperature oil), the flow of controlled chilling medium makes temperature in the fluidized-bed (1) between 110-175 ℃.The ratio of control hydrogenchloride and acetylene is 1.01-1.1, and the air speed of control acetylene was at 20-200 hour
-1
Behind the gas process catalyzer emulsion zone, the basic conversion fully, gas enters follow-up refining step through the pneumatic outlet (9) of cyclonic separator (8) and fluidized-bed (1).The part catalyzer is entered cyclonic separator (8) by gas-entrained, through its dipleg return catalizer emulsion zone.
Behind the catalyzer complete deactivation, can draw off from fluidized-bed (1) bottom by catalyst deactivation mouth (4).Catalyzer can be added in suitable period from catalyst inlet (7).
Embodiment 1
Member (6) is fixed on the heat transfer tube (5), inlet (2), gas distributor (3), catalyst outlet (4), heat transfer tube (5), catalyst inlet (7), the cyclonic separator (8) of gas are linked to each other with the barrel of fluidized-bed (1) successively with pneumatic outlet (9), and formation has complete fluidized-bed (1).Wherein, using pressure drop to account for the beds pressure drop is 20% tubular gas sparger; Adopting highly is the close phase height 200% of catalyzer, and sectional area is the heat transfer tube of bed sectional area 5%; The employing voidage is 90% member, and two interlayer crossing angle are 90 °, highly are 20% of fluidized-bed diameter; With interfloor distance is 10% of fluidized-bed diameter.Use granularity to be 0.1mm, specific surface area is 600m
2/ g, tap density is 1000kg/m
3The catalyzer that contains mercury chloride and tin chloride, with catalyzer from catalyst inlet (7) fluidized-bed (1) of packing into.In order to make catalyzer not stop up gas distributor (3), feed nitrogen by fluidized-bed gas inlet, bottom (2) through gas distributor (3) when adding catalyzer.Under the loosening effect of the less nitrogen of flow, granules of catalyst enters fluidized-bed from catalyst inlet 7, is deposited in the zone of gas distributor (3) top in the fluidized-bed (1).Catalyzer is all packed into behind the fluidized-bed (1), make the catalyzer in the fluidized-bed (1) be in fluidized state by the logical nitrogen of gas feed (2).In heat transfer tube (5), feed temperature greater than 120 ℃ saturation water, make the temperature in the fluidized-bed (1) be increased to 100-120 ℃ gradually.Feed hydrogenchloride and acetylene by gas inlet (2) gradually through gas distributor (3) then.Heat is emitted in reaction, and temperature is increased to 110-175 ℃ gradually in the fluidized-bed (1).In this process, the heat transferring medium in the heat transfer tube 6 switched to temperature less than 90 ℃ saturation water, the flow of controlled chilling medium, the temperature that makes fluidized-bed (1) catalyzer emulsion zone is at 110 ℃.The ratio of control hydrogenchloride and acetylene is 1.05, and the acetylene volume space velocity is 200 hours
-1Behind the gas process catalyzer emulsion zone, conversion of alkyne is 97.0%, and the vinylchlorid selectivity is 99.20%.
Gas enters follow-up refining step through the pneumatic outlet (9) of cyclonic separator (8) and fluidized-bed (1).The part catalyzer is entered cyclonic separator (8) by gas-entrained, through its dipleg return catalizer emulsion zone.
Member (6) is fixed on the heat transfer tube (5), inlet (2), gas distributor (3), catalyst outlet (4), heat transfer tube (5), catalyst inlet (7), the cyclonic separator (8) of gas are linked to each other with the barrel of fluidized-bed (1) successively with pneumatic outlet (9), and formation has complete fluidized-bed (1).Wherein, using pressure drop to account for the beds pressure drop is 35% board-like gas distributor; Adopting highly is the close phase height 100% of catalyzer, and sectional area is the heat transfer tube of bed sectional area 30%; The employing voidage is 50% member, and the crossing angle between two-layer member is 45 °, highly is 20% of fluidized-bed diameter; Layer member spacing is from being 1% of fluidized-bed diameter together.Use granularity to be 0.05mm, specific surface area is 1000m
2/ g, tap density is 300kg/m
3The catalyzer that contains mercury chloride and zinc chloride.With catalyzer from catalyst inlet (7) fluidized-bed (1) of packing into.In order to make catalyzer not stop up gas distributor (3), feed nitrogen by fluidized-bed gas inlet, bottom (2) through gas distributor (3) when adding catalyzer.Under the loosening effect of the less nitrogen of flow, granules of catalyst enters fluidized-bed from catalyst inlet 7, is deposited in the zone of gas distributor (3) top in the fluidized-bed (1).Catalyzer is all packed into behind the fluidized-bed (1), make the catalyzer in the fluidized-bed (1) be in fluidized state by the logical nitrogen of gas feed (2).In heat transfer tube (5), feed temperature greater than 120 ℃ saturation steam, make the temperature in the fluidized-bed (1) be increased to 100-120 ℃ gradually.Feed hydrogenchloride and acetylene by gas inlet (2) gradually through gas distributor (3) then.Heat is emitted in reaction, and temperature is increased to 110-175 ℃ gradually in the fluidized-bed (1).In this process, the heat transferring medium in the heat transfer tube 6 switched to temperature less than 90 ℃ mineral oil, the flow of controlled chilling medium, the temperature that makes fluidized-bed (1) catalyzer emulsion zone is at 130 ℃.The ratio of control hydrogenchloride and acetylene is 1.1, and the acetylene volume space velocity is 20 hours
-1Behind the gas process catalyzer emulsion zone, conversion of alkyne is 98.5%, and the vinylchlorid selectivity is 99.10%.
Gas enters follow-up refining step through the pneumatic outlet (9) of cyclonic separator (8) and fluidized-bed (1).The part catalyzer is entered cyclonic separator (8) by gas-entrained, through its dipleg return catalizer emulsion zone.
Member (6) is fixed on the heat transfer tube (5), inlet (2), gas distributor (3), catalyst outlet (4), heat transfer tube (5), catalyst inlet (7), the cyclonic separator (8) of gas are linked to each other with the barrel of fluidized-bed (1) successively with pneumatic outlet (9), and formation has complete fluidized-bed (1).Wherein, using pressure drop to account for the beds pressure drop is 30% float-valve type gas distributor; Adopting highly is the close phase height 150% of catalyzer, and sectional area is the heat transfer tube of bed sectional area 15%; The employing voidage is 70% member, and two interlayer crossing angle are 90 °, highly are 80% of fluidized-bed diameter; With interfloor distance is 10% of fluidized-bed diameter.Use granularity to be 0.3mm, specific surface area is 1200m
2/ g, tap density is 600kg/m
3The catalyzer that contains mercury chloride and Manganous chloride tetrahydrate.With catalyzer from catalyst inlet (7) fluidized-bed (1) of packing into.In order to make catalyzer not stop up gas distributor (3), feed nitrogen by fluidized-bed gas inlet, bottom (2) through gas distributor (3) when adding catalyzer.Under the loosening effect of the less nitrogen of flow, granules of catalyst enters fluidized-bed from catalyst inlet 7, is deposited in the zone of gas distributor (3) top in the fluidized-bed (1).Catalyzer is all packed into behind the fluidized-bed (1), make the catalyzer in the fluidized-bed (1) be in fluidized state by the logical nitrogen of gas feed (2).In heat transfer tube (5), feed temperature greater than 120 ℃ mineral oil, make the temperature in the fluidized-bed (1) be increased to 100-120 ℃ gradually.Feed hydrogenchloride and acetylene by gas inlet (2) gradually through gas distributor (3) then.Heat is emitted in reaction, and temperature is increased to 110-175 ℃ gradually in the fluidized-bed (1).In this process, the heat transferring medium in the heat transfer tube 6 switched to temperature less than 90 ℃ air, the flow of controlled chilling medium, the temperature that makes fluidized-bed (1) catalyzer emulsion zone is at 150 ℃.The ratio of control hydrogenchloride and acetylene is 1.05, and the acetylene volume space velocity is 100 hours
-1Behind the gas process catalyzer emulsion zone, conversion of alkyne is 98.3%, and the vinylchlorid selectivity is 99.14%.
Gas enters follow-up refining step through the pneumatic outlet (9) of cyclonic separator (8) and fluidized-bed (1).The part catalyzer is entered cyclonic separator (8) by gas-entrained, through its dipleg return catalizer emulsion zone.
Member (6) is fixed on the heat transfer tube (5), inlet (2), gas distributor (3), catalyst outlet (4), heat transfer tube (5), catalyst inlet (7), the cyclonic separator (8) of gas are linked to each other with the barrel of fluidized-bed (1) successively with pneumatic outlet (9), and formation has complete fluidized-bed (1).Wherein, using pressure drop to account for the beds pressure drop is 35% tubular gas sparger; Adopting highly is the close phase height 100% of catalyzer, and sectional area is the heat transfer tube of bed sectional area 12%; The employing voidage is 90% member, and two interlayer crossing angle are 60 °, highly are 100% of fluidized-bed diameter; With interfloor distance is 20% of fluidized-bed diameter.Use granularity to be 0.5mm, specific surface area is 900m
2/ g, tap density is 500kg/m
3Contain mercury chloride and copper chloride catalyst.With catalyzer from catalyst inlet (7) fluidized-bed (1) of packing into.In order to make catalyzer not stop up gas distributor (3), feed nitrogen by fluidized-bed gas inlet, bottom (2) through gas distributor (3) when adding catalyzer.Under the loosening effect of the less nitrogen of flow, granules of catalyst enters fluidized-bed from catalyst inlet 7, is deposited in the zone of gas distributor (3) top in the fluidized-bed (1).Catalyzer is all packed into behind the fluidized-bed (1), make the catalyzer in the fluidized-bed (1) be in fluidized state by the logical nitrogen of gas feed (2).In heat transfer tube (5), feed temperature greater than 120 ℃ air, make the temperature in the fluidized-bed (1) be increased to 100-120 ℃ gradually.Feed hydrogenchloride and acetylene by gas inlet (2) gradually through gas distributor (3) then.Heat is emitted in reaction, and temperature is increased to 110-175 ℃ gradually in the fluidized-bed (1).In this process, the heat transferring medium in the heat transfer tube 6 switched to temperature less than 90 ℃ air, the flow of controlled chilling medium, the temperature that makes fluidized-bed (1) catalyzer emulsion zone is at 175 ℃.The ratio of control hydrogenchloride and acetylene is 1.05, and the acetylene volume space velocity is 50 hours
-1Behind the gas process catalyzer emulsion zone, conversion of alkyne is 98.7%, and the vinylchlorid selectivity is 99.20%.
Member (6) is fixed on the heat transfer tube (5), inlet (2), gas distributor (3), catalyst outlet (4), heat transfer tube (5), catalyst inlet (7), the cyclonic separator (8) of gas are linked to each other with the barrel of fluidized-bed (1) successively with pneumatic outlet (9), and formation has complete fluidized-bed (1).Wherein, using pressure drop to account for the beds pressure drop is 25% tubular gas sparger; Adopting highly is the close phase height 200% of catalyzer, and sectional area is the heat transfer tube of bed sectional area 8%; The employing voidage is 80% member, and two interlayer crossing angle are 90 °, highly are 100% of fluidized-bed diameter; With interfloor distance is 5% of fluidized-bed diameter.Use granularity to be 0.4mm, specific surface area is 800m
2/ g, tap density is 450kg/m
3Contain mercury chloride and Lanthanum trichloride catalyzer.With catalyzer from catalyst inlet (7) fluidized-bed (1) of packing into.In order to make catalyzer not stop up gas distributor (3), feed nitrogen by fluidized-bed gas inlet, bottom (2) through gas distributor (3) when adding catalyzer.Under the loosening effect of the less nitrogen of flow, granules of catalyst from catalyst inlet 7 fluidized-bed of packing into, is deposited in the zone of gas distributor (3) top in the fluidized-bed (1).Catalyzer is all packed into behind the fluidized-bed (1), make the catalyzer in the fluidized-bed (1) be in fluidized state by the logical nitrogen of gas feed (2).In heat transfer tube (5), feed temperature greater than 120 ℃ air, make the temperature in the fluidized-bed (1) be increased to 100-120 ℃ gradually.Feed hydrogenchloride and acetylene by gas inlet (2) gradually through gas distributor (3) then.Heat is emitted in reaction, and temperature is increased to 110-175 ℃ gradually in the fluidized-bed (1).In this process, the heat transferring medium in the heat transfer tube 6 switched to temperature less than 140 ℃ water, the flow of controlled chilling water, the temperature that makes fluidized-bed (1) catalyzer emulsion zone is at 175 ℃.The ratio of control hydrogenchloride and acetylene is 1.01, and the acetylene volume space velocity is 30 hours
-1Behind the gas process catalyzer emulsion zone, conversion of alkyne is 97.5%, and the vinylchlorid selectivity is 99.30%.
Claims (13)
1, a kind of hydrogenchloride and acetylene reaction prepare the fluidized-bed reactor of vinylchlorid, it is characterized in that, this reactor comprises:
(a) fluidized-bed (1);
(b) one is arranged on the reaction raw materials gas inlet (2) of fluidized-bed (1) bottom and the gas distributor (3) that is arranged on this inlet top;
(c) heat transfer tube (5) that is arranged on gas distributor (3), heat transfer tube (5) links to each other with the barrel of fluidized-bed (1);
(d) member (6) that is fixed on the heat transfer tube (5);
(e) one group is arranged on fluidized-bed top, is used for the cyclonic separator (8) of catalyst recovery, and cyclonic separator (8) is fixed on the barrel on fluidized-bed (1) top;
(f) reaction gas outlet (9) that is arranged on fluidized-bed top, this outlet links to each other with cyclonic separator (8);
(g) catalyzer that is arranged on the fluidized-bed middle part adds inlet (7), and this adds inlet and links to each other with the barrel of fluidized-bed (1);
(h) the shifting out an of spent catalyst that is arranged on fluidized-bed bottom mouthful (4), this barrel that shifts out mouthful bottom fluidized-bed (1) links to each other.
2, a kind of hydrogenchloride according to claim 1 and acetylene reaction prepare the fluidized-bed reactor of vinylchlorid, it is characterized in that, described reactor comprises a plurality of heat transfer tubes (5) that are arranged on gas distributor (3), and heat transfer tube (5) links to each other with the barrel of fluidized-bed (1).
3, a kind of hydrogenchloride according to claim 1 and acetylene reaction prepare the fluidized-bed reactor of vinylchlorid, it is characterized in that, described reactor comprises a plurality of members (6) that are fixed on the heat transfer tube (5).
4, a kind of hydrogenchloride according to claim 1 and acetylene reaction prepare the fluidized-bed reactor of vinylchlorid, it is characterized in that, group was arranged on fluidized-bed top more than described reactor comprised, be used for the cyclonic separator (8) of catalyst recovery, cyclonic separator (8) is fixed on the barrel on fluidized-bed (1) top.
5, a kind of hydrogenchloride according to claim 1 and acetylene reaction prepare the fluidized-bed reactor of vinylchlorid, it is characterized in that, described gas distributor is any in variable mass drift tube type sparger, multiaperture-type sparger, the float-valve type sparger.
6, a kind of hydrogenchloride according to claim 1 and acetylene reaction prepare the fluidized-bed reactor of vinylchlorid, it is characterized in that, the bottom of described heat transfer tube is 50～300mm apart from the distance of gas distributor.
7, a kind of hydrogenchloride according to claim 1 and acetylene reaction prepare the fluidized-bed reactor of vinylchlorid, it is characterized in that, the height of described heat transfer tube is 100%～200% of a catalyzer emulsion zone static height, and the sectional area of heat transfer tube accounts for 5%～30% of fluidized-bed sectional area.
8, a kind of hydrogenchloride according to claim 1 and acetylene reaction prepare the fluidized-bed reactor of vinylchlorid, it is characterized in that, described member is the member of horizontal positioned, be fixed on the heat transfer tube, its porosity is 50%-90%, adjacent two-layer member cross arrangement, and intersecting angle is 45 °-90 °, height between two-layer member is the 20%-100% of fluidized-bed diameter, is the 1%-20% of fluidized-bed diameter with the distance between layer member.
9, a kind of hydrogenchloride and acetylene reaction prepare the method for vinylchlorid, it is characterized in that, this method comprises the steps:
(1) member (6) is fixed on the heat transfer tube (5), inlet (2), gas distributor (3), catalyst outlet (4), heat transfer tube (5), catalyst inlet (7), the cyclonic separator (8) of gas are linked to each other with the barrel of fluidized-bed (1) successively with pneumatic outlet (9), constitute a complete fluidized-bed (1) reactor;
(2) catalyzer is added fluidized-bed (1) from catalyst inlet (7), feed nitrogen or air by fluidized-bed gas inlet, bottom (2) through gas distributor (3) when adding catalyzer, down loosening at less nitrogen of flow or air, granules of catalyst enters fluidized-bed from catalyst inlet 7, be deposited in the zone of gas distributor (3) top in the fluidized-bed (1), the static loading height of catalyzer is 3～10 times of fluidized-bed diameter;
(3) catalyzer is all packed into behind the fluidized-bed (1), make the catalyzer in the fluidized-bed (1) be in fluidized state by the logical rare gas element of gas feed (2); In heat transfer tube (5), feed the high temperature heat transferring medium, make the temperature in the fluidized-bed (1) be increased to 100～120 ℃ gradually;
(4) fed the gas mixture of hydrogenchloride and acetylene by gas inlet (2) and sparger (3) in fluidized-bed (1), control hydrogenchloride is 1.01: 1～1.1: 1 with the mol ratio of acetylene, and the interior volume space velocity of fluidized-bed is 20～200Nm
3Acetylene/m
3Catalyzer/hour; Heat is emitted in reaction, and temperature is increased to 110～175 ℃ gradually in the fluidized-bed (1);
(5) heating medium with heat transfer tube (5) switches to heat-eliminating medium, the place of (1) catalyst buildup in the control fluidized-bed, hereinafter to be referred as the catalyzer emulsion zone, temperature between 110～175 ℃;
(6) behind acetylene and the hydrogenchloride process catalyzer emulsion zone, almost be converted into vinylchlorid fully; A spot of unreacted acetylene and hydrogenchloride and a large amount of vinylchlorid gas, process cyclonic separator (8) goes out fluidized-bed from the pneumatic outlet (9) of fluidized-bed, enters follow-up tripping device;
Part catalyzer in the catalyzer emulsion zone is carried by air-flow, enters cyclonic separator (8), and the bottom of process cyclonic separator (8) is back to the catalyzer emulsion zone;
(7) behind catalyst deactivation, discharge from the outlet (4) of fluidized-bed (1) bottom; Add catalyzer from catalyst inlet (7) to fluidized-bed (1) simultaneously, the assurance process is moved continuously.
10, a kind of hydrogenchloride according to claim 7 and acetylene reaction prepare the method for vinylchlorid, it is characterized in that, described catalyst particle size is 0.05～0.5mm, and specific surface area is 600～1200m
2/ g, tap density is 300～1000kg/m
3, intensity is greater than the muriatic catalyzer of the containing metal of ball milled 70%; Described metal chloride is the muriate of mercury, the muriate of tin, the muriate of copper, the muriate of zinc, the muriate of manganese, any in the muriate of lanthanum.
11, a kind of hydrogenchloride according to claim 7 and acetylene reaction prepare the method for vinylchlorid, it is characterized in that what described high temperature heat transferring medium was a temperature greater than in 120 ℃ high-temperature water, high-temperature steam, high temperature inert gas or the high temperature oil is any or multiple.
12, a kind of hydrogenchloride according to claim 7 and acetylene reaction prepare the method for vinylchlorid, it is characterized in that, described heat-eliminating medium is any or multiple of water, gas or oil.
13, a kind of hydrogenchloride according to claim 7 and acetylene reaction prepare the method for vinylchlorid, it is characterized in that, described gas distributor pressure drop is the 20%-35% of beds total pressure drop.
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| CN101613251B (en) * | 2009-07-15 | 2012-07-18 | 仇晓丰 | Method for synthesizing chloroethylene |
| CN102675035A (en) * | 2012-06-11 | 2012-09-19 | 上海中科高等研究院 | Method for preparing vinyl chloride from acetylene and dichloroethane |
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| CN101940898B (en) * | 2010-09-26 | 2012-09-19 | 河北科技大学 | Method for recycling silicon tetrachloride |
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| CN104326867B (en) * | 2014-10-16 | 2016-03-16 | 中科易工（上海）化学科技有限公司 | A kind of acetylene and ethylene dichloride catalyze and synthesize the separation and recovery method of vinylchlorid in process for vinyl chloride tail gas without mercury |
| CN105910934A (en) * | 2016-06-24 | 2016-08-31 | 陕西延长石油（集团）有限责任公司 | Strength property evaluating device suitable for solid granular catalyst |
| CN110180469A (en) * | 2019-05-20 | 2019-08-30 | 陕西金泰氯碱化工有限公司 | A kind of reaction control method catalyzing and synthesizing vinyl chloride with gas permeable member optimization mercury-free |
| CN113121303A (en) * | 2021-04-26 | 2021-07-16 | 河北美邦工程科技股份有限公司 | Chloroethylene production process and special device thereof |
| CN113121303B (en) * | 2021-04-26 | 2023-03-24 | 河北美邦工程科技股份有限公司 | Chloroethylene production process and special device thereof |
| CN113617298A (en) * | 2021-06-29 | 2021-11-09 | 中国成达工程有限公司 | Method for producing chloroethylene by acetylene method |
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