CN1106058A - Technology and its equipment for preparation of liquid petroleum gas using decyclized C5 as main raw material - Google Patents

Abstract

The process for preparing liquid petroleum gas by "critical adsorption" features use of the mixture of decyclized C5 and additive as adsorbent and nitrogen and/or CO2 as adsorbent. Said additive contains disperser (0.05-0.1%), anti-explosion agent (0.01-0.025), diluent (0.5-10%) and antistatic agent (0.01-0.025%). The new civil fuel has the advantages of simple preparing process, low cost and high safety.

Description

Technology and its equipment for preparation of liquid petroleum gas using decyclized C5 as main raw material

The present invention relates to a kind of is the technology that main raw material is produced liquefied petroleum gas with division ring carbon five, and special-purpose production unit.

China adopts heavier cracking stocks such as solar oil or petroleum naphtha to carry out ethylene production mostly, and the quantity of its by-product carbon five is more, and normally 14%～17% of ethylene yield.Owing to be subjected to restrictions such as its production or technology, the most of so far carbon five of China is still made industrial fuel and is burnt.

For this reason, it is main composition with carbon five lightweight oils such as grade that the people is arranged, and is ancillary component with vaporization agent, additive I, additive II, through the auxiliary material synthetic liquid fuel, to solve the problem (number of patent application 921042345, applying date 92.5.31) that it is difficult that the both urban and rural residents burns gas; But its shortcoming is: because of light crude oil carbon content height, be easy to knot carbon when preheating is gasified, and cause the obstruction pipeline during use, cause an explosion accident etc.

Application number 92103434 discloses a kind of employing pressurized air and has made C 5 vaporisation, and by its concentration of electrical equipment control and pressure, makes the air-flow of air pressure remain stable concentration and pressure, and the form with pipeline directly flows to user's use again.

Although it has adopted comparatively simple technology, making pentane (C5) be converted into the universal pipes combustion gas becomes possibility; But because its pipe gas generation equipment is made up of fuel tank, air compressor, combustable gas concentration mensuration sensing head and density control valve, well heater and temperature control element, electric control box, gas pressure regulating box and air shooter thereof etc. at least.Therefore, equipment is complicated, and it is bigger consume energy, especially because its directly adopts the air that contains a large amount of oxygen, makes carbon five after the gasification and its thorough mixing and is easy to set off an explosion, and its consequence is hardly imaginable.

In addition, the patent of invention of Nanjing University's oil gasification liquid fuel and production technique thereof (application number 91104405.1).It is to adopt thermopolymerization to remove the prepared decylization carbon five of cyclopentadiene to be main raw material, add stoppers such as Resorcinol then, entrainers such as methyl alcohol, thinners such as light sherwood oil, also add detonation suppressor and static inhibitor etc. in addition, make by its prescription and five allotments of division ring carbon.By its technology and method is fully feasible; But, when preparing gasification liquid fuel by the embodiment ratio requirement, both made about envrionment temperature to 36 ℃, vaporization rate voluntarily about 60% is also only arranged, can not no raffinate, do not reach the purpose of replacement liquid liquefied oil gas, and its production cost is higher, and also difficulty can be applied.

It is simple to the purpose of this invention is to provide a kind of technology, convenient, the safety of preparation, with low cost, finished product can not need the bubbling pressurization or to preheating of fuel under normal temperature environment, can gasify the production technique of comparatively uniform liquefied petroleum gas of phase before and after the thermal value from line stabilization.

Another object of the present invention provides a kind of rational in infrastructure, less investment, and floor space is little, and energy consumption is low, and work efficiency is higher, operating safety, produces the specific equipment of liquefied petroleum gas reliably.

Major scheme of the present invention is: with nitrogen and/or carbonic acid gas is adsorbate, with the C5 fraction of engineering by-products such as ethene, the mixture of prepared division ring carbon five and additive is that sorbent material carries out the liquefied petroleum gas that " critical adsorption " makes " out-phase vapor of mixture body " after the decylization art breading.Described " critical adsorption " is the adsorbate nitrogen and/or the carbonic acid gas of compression, after inputing to a container (as the critical adsorption retort), enter the spray chamber along a plurality of (for example dozens of) micropore, make it adsorbate and produce sufficiently high gas velocity, the static pressure at fog nozzle centre hole position is fallen form " venturi-effect " in nearly vacuum.At this moment, the division ring carbon Wuyuan material that is mixed with additive in advance is at compressed nitrogen, under the effect of carbonic acid gas, be inhaled into the fog nozzle centre hole, converge at Venturi meter head and effusive pressurized gas from micropore, carbon Wuyuan material promptly is compressed gaseous fraction and smashes into uneven liquid grain, sprayed by fog nozzle together, deliver to the space of " critical adsorption " reactor, the liquid light hydrocarbon raw material forms the countless liquid levels that differ in size at space reactor, and material is among the process of critical phase transformation, and its molecule chain is elongated, viscosity reduces, specific surface area increases, and has gaseous state and liquid dual physico-chemical property, and its microtexture is similar to organic Guan Nengtuan.The molecule chain can be considered two-dimentional interface, and the aperture is similar to the aperture of solid adsorbent about 0.62 millimicron the order of magnitude.Analyze from physicochemical principle, absorption occurs in the surface, and the liquid grain is got more little surface and also become big more, and loading capacity is also big more.The mechanism that has possessed sorbent material in view of the light hydrocarbon component under the above-mentioned condition.Though and the inorganic substance nitrogen, carbonic acid gas virgin state and the physico-chemical property that are under the equal conditions are different with light hydrocarbon component, and they belong to apolar substance, moment of dipole all is zero, known to the possible condition of dissolution phenomena, polar solvent dissolves polar material easily, non-polar solvent dissolves the principle of apolar substance easily, and inorganic nitrogen, carbonic acid gas and the organically association of the intermolecular easy trigger molecule of lighter hydrocarbons are for the two dissolving, absorption, azeotropic have been created condition.Therefore, nitrogen, carbonic acid gas have possessed the mechanism of adsorbate equally.

In sum, be in the sorbent material-5C light hydrocarbon cut under " critical phase transformation " state, do irregular motion with the speed of 300～400M/S in " critical adsorption " reactor, nitrogen, carbonic acid gas (its molecular radius is 0.74nm) that the two-dimentional interface in its molecule chain (aperture is about 0.62nm) at first is subjected to adsorbate collide opportunity with 6,500,000,000 times/second the order of magnitude.Make the two-dimentional interface in the sorbent molecule chain that capillarity take place, produce the aggegation of adsorbate kapillary.Around the liquid grain of sorbent material, form film spreading simultaneously again automatically, the variation of Gibbs free energy has taken place again in the film spreading process, and make the liquid grain because action of gravity crashes into " critical adsorption " reactor bottom, finished the production process of " out-phase vapor of mixture component ".Said process ties up under the normal temperature condition and finishes.

Above-mentioned " critical adsorption " process can be to carry out in 0.05: 99.95～12: 88 usually by the ratio of adsorbate and sorbent material, and the pressure in described " critical adsorption reaction " is 0.02～2.5KG/CM ²; Its preferable absorption is 1: 99～5: 95 with the ratio of sorbent material, and the pressure in the critical adsorption retort is 1.5～2.0KG/CM ²Wherein, described adsorbate can be a kind of one-component in nitrogen or the carbonic acid gas, also can the two mixture.

In described division ring carbon five, still contain a spot of isoprene etc., then add dispersion agent, specifically can adopt Sodium Nitrite, nitrosamine and analogue thereof because of 0.05～0.1% ratio in additive in its content.

In addition, in order further to improve security, stability and the work efficiency etc. of technological process, can add one or more components in following in additive: detonation suppressor is 0.01～0.025%(and the ratio of the weight of carbon five, down with); Thinner 5～10%; Water is 5～10%; Antistatic agent is 0.01～0.025%.The concrete material that uses is selected by concrete composition of expecting with the carbon Wuyuan and raw material sources etc.For example, detonation suppressor can be selected ferrocene, tetraethyllead, nitro class and analogue thereof for use; Thinner can be used ether, acetone and analogue thereof; Antistatic agent is polyoxyethylene, alkyl sodium salicylate and analogue thereof etc.

In addition, can in production, storing, use, in time discover may leaking of liquefied petroleum gas, also can add the stink agent (as ethanethio etc.) about 0.01% therein in order to make user or manufacturing enterprise etc.

Realize technology of the present invention can adopting following specific equipment in order to be beneficial to: one or several are arranged, near the bottom (bottom) of tank body by being arranged on the critical spray assembly that critical spraying seat on the tank body and critical fog-spray nozzle provided thereon constitute; And the fluid orifice that on described critical fog-spray nozzle, is provided with the static pressure generation chamber and communicates with inlet pipe.Described fluid orifice can directly communicate with inlet pipe one by one, also can be provided with a uniform chamber of cyclic between critical spraying seat and critical fog-spray nozzle, evenly is provided with several in order to link up the fluid orifice of uniform chamber and static pressure generation chamber on critical fog-spray nozzle; And the liquid-inlet pipe that is positioned at critical fog-spray nozzle middle part also is opened on static pressure generation chamber place.

Usually, be arranged near the tank base critical spray assembly by parts such as stake bodies, its injection direction can also can be certain oblique angle with the axial line of tank body and upwards spray vertically upward; Be positioned near the tank base or the jet orifice of middle and lower part, also can it be established near the tank body middle part through stake body.In addition, the bore of described liquid-phase tube and the bore of fluid orifice are then decided by separately be provided with hole count, flow and design output thereof etc. respectively.For example, the middle-size and small-size equipment of per unit area yield 50～100kg per hour, the bore of its liquid-phase tube is Φ 1.0～1.5mm, and the bore in gas jet hole is 0.5～1.0mm.

Hence one can see that, production process of the present invention, and in fact promptly described sorbent material and adsorbate have the mechanism that absorbs and extract and deposit through the technological process of " critical adsorption "; And its goods from the explanation of getting on of the viewpoint of chemical industry absorption, not can be considered and are both the fluidic compounding substances by the sorbent material of desorb and adsorbate.

On the other hand, the use of the liquefied petroleum gas (LPG) of " the out-phase vapor of mixture body " produced by the present invention then can be regarded as the desorption process in the chemical adsorbing separation technology, also can be regarded as the reduction process of material.Because under certain conditions-and the aggegation liquid of nitrogen and/or carbon dioxide by the molecular chain aggegation of light hydrocarbon component, is subjected to the influence that gibbs freely becomes owing to sprawl process again, aggegation liquid is enclosed in inside the liquid grain; Because two kinds of materials of gas-liquid are temporary transient under certain condition and deposit, if in case change its existence condition-pressure, temperature, volume, so the two separation will take place.The use of " liquefied petroleum gas " allows gaseous state aggegation liquid make carrier exactly, and the 5C light hydrocarbon component is delivered to burner with gaseous state, and its delivery pressure can be 0.36～0.027kgf/cm ²Discharge velocity can be 1～1.5m/s, flow can be: 0.15kg/h, with about 1: 40＜volume oxygen〉ratio requirement for lighting, specifically: about 1: 17＜volume of primary air inlet oxygen, about 1: 23＜volume of secondary air inlet oxygen 〉, light the back light-hydrocarbon fuel for burning use, nitrogen, carbonic acid gas be situated between suction, decompose, distribute in air, finished desorption process, reached fluent meterial and gasified voluntarily, and for the purpose of burning and using.

By the liquefied petroleum gas that technology of the present invention is produced, after measured, the content standard of combustionproperty and burning back nuisance all is better than liquefied petroleum gas (LPG), piped gas, meets domestic gas standard and environmental requirement fully.

1, combustionproperty:

The liquefied petroleum gas liquefied petroleum gas (LPG) of this suction

Thermal load: 3000kcal/h 2000kcal/h

Consumption liquid measure: 0.25kg/h 0.45kg/h

Thermal value: 838.80kcal/mol 682.84Kcal/mol

Temperature of combustion: 950 ℃ 700 ℃

All the other indexs are identical with liquefied petroleum gas (LPG).

2, raffinate amount:＜5%

3, sulphur content content:＜0.02%.

Utilize prescription of the present invention and production technique, can make 400,000 tons of fuel of C5 fraction of China's ethylene project year by-product become one of civilian main fuel, reach the limited amount that remedies because of liquefied petroleum gas (LPG), can't meet the need of market, slow resident Jie uses the combustion gas difficulty, improves the town and country atmospheric pollution, provide a technology simple, preparation is convenient, and requiring less investment while yielding quicker results has the new variety of very high economic worth.

In addition, adopting the prepared liquefied petroleum gas of technology of the present invention can be enclosed in pressure is 1.5KG/CM ²～3KG/CM ²Steel and in, store, transport, use.Because of its filling pressure is starkly lower than existing liquefied petroleum gas (LPG) 10KG/CM ²Pressure.Therefore, it is more more convenient than liquefied petroleum gas (LPG) also to have a storage, transportation, can, use safer, the more difficult accident of sewing.

The present invention compared with prior art has many advantages: 1, technological line uniqueness, and technical process is reasonable, compact equipment, volume is small and exquisite, builds up this device of producing 150 tons of scales per year, only needs 20 square metres and gets final product; 2, work efficiency height, energy consumption are low, the scale of per hour producing the 66KG liquefied petroleum gas, and only consumption is for about 3.5KW; 3, need not adopt chemical industry equipment commonly used such as high pressure vessel, water distilling apparatus, whole device is safe and reliable, and is simple to operate, only need regularly fuel, raw material promptly sustainable production; 4, save energy turns waste into wealth, and reduces and pollutes; 5, not only have combustionproperties such as fuel gases calorific value height (higher by 30% than liquefied petroleum approximately) thermal load, temperature of combustion with the prepared product of Processes and apparatus of the present invention and all be higher than liquefied petroleum gas (LPG) and characteristics such as nontoxic, smokeless, pollution-free, and need not to use special-purpose stove and accessory, be applicable to the liquefaction burner (as liquefaction stove, water-heater etc.) of existing various models, specification; 6, during the present invention was particularly suitable for, the resident of zonule and enterprise used, and have less investment, last detective, the products made thereby saturation vapour pressure is lower, storing, canned, use all comparatively conveniently, be easy to popularization.Therefore, have very big society and economic benefit.

Below in conjunction with embodiment and accompanying drawing, the present invention is further described.

Accompanying drawing 1-a kind of structural representation of the present invention

The local amplification view of accompanying drawing 2-Figure 1A portion

In the following concrete proportioning that exemplifies, be basic raw material all with division ring carbon five, remaining various component, except that the addition of stopper (as Sodium Nitrite, inferior ammonium nitrate etc.) was the percentage ratio of the isoprene weight that contained among the C5, all the other additions were the percentage ratio of C5 weight.

Example 1: nitrogen: 0.05; Sodium Nitrite: 0.1; Ferrocene: 0.02; Ether: 5; Water: 5; Polyoxyethylene: 0.01; Ethanethio: 0.01.

Example 2: carbonic acid gas: 3.2; Nitrosamine: 0.05; Tetraethyllead: 0.01;

Acetone: 10; Water: 10; Alkyl sodium salicylate: 0.025; Ethanethio: 0.025.

Example 3: nitrogen: 1.5; Sodium Nitrite: 0.07; Tetraethyllead: 0.025; Acetone: 8; Water: 7; Alkyl sodium salicylate 0.015; Ethanethio 0.005.

Example 4: nitrogen: 8, carbonic acid gas 5.2; Nitrosamine: 0.09; Ferrocene: 0.025; Ether: 7; Water: 8; Polyoxyethylene: 0.02; Ethanethio: 0.015.

Example 5: nitrogen: 0.74; Sodium Nitrite: 0.09; Nitro class: 0.01; Acetone: 9; Water: 6, alkyl sodium salicylate: 0.01; Ethanethio: 0.01.

Example 6: nitrogen: 0.1; Sodium Nitrite: 0.06; Nitro sodium: 0.02; Acetone: 7; Water: 10; Polyoxyethylene 0.025; Ethanethio: 0.01.

Example 7: nitrogen: 4.0; Carbonic acid gas: 1.5; Nitrosamine: 0.08; Ether: 6; Water: 7; Alkyl sodium salicylate: 0.015; Ethanethio: 0.01.

Example 8: carbonic acid gas: 0.5; Sodium Nitrite: 0.08; Ferrocene: 0.03; Acetone: 8; Water: 5; Polyoxyethylene: 0.015; Ethanethio: 0.01.

Specifically can implement like this referring to the utility model shown in accompanying drawing 1 and the accompanying drawing 2:

Be processed into the critical fog-spray nozzle (12) that is similar to Y type rotator with copper rod turning, be respectively equipped with tubing (9) and static pressure generation chamber (11) on its axis, and be provided with six Φ 0.8mm fluid orifices (13) by expansion portion place's radial equipartition; Critical spraying seat (10) is then made copper U type rotator, and both adopt screw thread to spin to match, form a uniform chamber of cyclic (14) therebetween; It communicates with static pressure generation chamber (11) through fluid orifice (13), is connected with pneumatic tube (7) by the duct of being located on the critical spraying seat (10) (17) simultaneously.The critical spray assembly (20) that assembles thus; By being bolted on the stake body (15), the latter then with electric welding directly and tank body (2) be welded into one.In addition, tank body (2) bottom in stake body (15) one sides is provided with a production tube (16); On the top of tank body, then be provided with a tracheae (3), compressed machine of the latter (4) and knockout drum (5) and valve (22) link to each other required gas again with pneumatic tube (7).

Like this, by compressor (7) adsorbate (as N2) is pressurized to 3kg/cm ²About, through gas, liquid separating tank (4) and valve (22), insert the inlet pipe (7) of critical adsorption reacting tank body (2), and make inorganic gas thus through the uniform chamber of ring-type (14), while high speed six fluid orifices of flow path (13), concentrate and meet at static pressure generation chamber (11), its pressure is promptly reduced to vacuum, forms " venturi-effect "; At this moment, coupled liquid-inlet pipe (9) sucks additive described in the foregoing description and division ring carbon Wuyuan material voluntarily, and under the intersection of high velocity air is impacted, division ring carbon Wuyuan material as adsorbate is crashed to pieces into uneven fine liquid grain, be vaporific and spray in the critical adsorption reacting tank body (2), carry out physical and chemical effect fully.Unnecessary Gas Phase Adsorption matter is collected by tank body top, and, liquid separating tank (5) gentle by the compressed machine of muffler (3) (4), the gaseous state adsorbate is pressed into again inlet pipe (7) again and recycles, insufficient section is inserted by pipe (23), and a spot of liquid then separates the back and discharged by pipe (6); The prepared out-phase azeotropic of absorption reaction liquid grain then crashes into the bottom of critical adsorption reacting tank body (2) under action of gravity, and collects through production tube (16), and is canned.

Claims (10)

1, a kind of is the technology that main raw material is produced liquefied petroleum gas with division ring carbon five, it is characterized in that: the mixture with division ring carbon five and additive is a sorbent material, with be adsorbate with nitrogen and/or carbonic acid gas, carry out " critical absorption " and make the liquefied petroleum gas of " out-phase vapor of mixture body ".

2, the production technique of liquefied petroleum gas as claimed in claim 1 it is characterized in that the described adsorbate and the ratio of sorbent material are 0.05: 99.95～12: 88, and both is 0.02～2.5KG/cm at pressure ²Condition under carry out " critical adsorption ".

3, the production technique of liquefied petroleum gas as claimed in claim 2 it is characterized in that the described adsorbate and the ratio of sorbent material are 1: 99～5: 95, and both is at 1.5～2.0KG/CM ²Pressure range in carry out " critical adsorption ".

4, as the production technique of the described liquefied petroleum gas of claim 1 to 3, it is characterized in that described additive is a dispersion agent, its interpolation scope be in the raw material isoprene content 0.05～0.1%.

5, the production technique of liquefied petroleum gas as claimed in claim 4 is characterized in that also containing in the described additive detonation suppressor: 0.01～0.025(C5 raw materials quality, down together); Thinner: 5～10%; Water: 5～10%; Antistatic agent; 0.01～0.025%.

6, the production technique of liquefied petroleum gas as claimed in claim 4 is characterized in that described dispersion agent is Sodium Nitrite, nitrosamine.

7, the production technique of liquefied petroleum gas as claimed in claim 5 is characterized in that: detonation suppressor is ferrocene, tetraethyllead, nitro class; Thinner is ether, acetone; Antistatic agent is polyvinyl chloride, alkyl sodium salicylate.

8, a kind of is the critical adsorption conversion unit that main raw material is produced liquefied petroleum gas with carbon five, comprise tank body and transfer line, it is characterized in that, be provided with one or several critical spray assemblies (20) in the bottom of tank body (2), it is to be made of the critical spraying seat (10) and the critical fog-spray nozzle (12) provided thereon that are arranged on the tank body (2), and the fluid orifice (13) that is provided with static pressure generation chamber (11) and communicates with inlet pipe (9) on described critical fog-spray nozzle (12).

9, critical adsorption conversion unit as claimed in claim 8, it is characterized in that between described critical spraying seat (10) and critical fog-spray nozzle (12), be provided with a uniform chamber of cyclic (14), and all establish the fluid orifice (13) that several are used to link up uniform chamber (14) and static pressure generation chamber (11) on critical fog-spray nozzle (12), the liquid-inlet pipe (9) that is positioned at critical fog-spray nozzle middle part also is opened on static pressure generation chamber (11) and locates.

10, critical adsorption conversion unit as claimed in claim 8 or 9 is characterized in that the top of described tank body (2) is provided with muffler (3); Be provided with production tube (16) near the bottom of tank body (2).

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