Method for preparing hydrogen

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for producing hydrogen and carbon dioxide. Method involves the following steps: (a) oxidation of solid substance in the first reaction zone to obtain hydrogen; (b) transfer of oxidized form of a solid substance to other reaction zone wherein a reducing agent flow is fed chosen from hydrocarbons, and its reaction with a reducing agent flow to obtain carbon dioxide; (c) extraction of a solid substance reduced form and its feeding to the first reaction zone. Heat is supplied using additional block for maintenance the temperature regimen disposed between two reaction zones and by using heat formed in the further oxidation of solid substance with air. Heat is supplied during one of the following processes preferably: (b) or (c). Used solid substance has no at least one oxidative-reductive member as a binary compound. Proposed invention provides enhancing effectiveness of process based on supplying heat to reaction zones using the additional block.

EFFECT: improved preparing method.

30 cl, 5 dwg, 6 tbl, 11 ex

 

This invention relates to a method of producing hydrogen, which essentially consists in that the solid is subjected to oxidation, and thus obtained oxidized form is treated with a hydrocarbon; total reaction leads to the formation of hydrogen or substances, which can be easily converted to hydrogen and CO2that get in the flow in a high concentration, which can be removed in the pumped tank or into the ocean.

It is known that hydrogen is formed as the product of numerous chemical reactions, some of which are used to obtain it. In ways, more interesting from the industrial point of view, the process begins with hydrocarbons or coal. The hydrogen is produced from hydrocarbons by various processes of pyrolysis and cracking, and primarily in refineries with catalytic reforming or chemicals from synthesis gas (CO+H2), which, in turn, is obtained by reaction of hydrocarbons with steam (steam reforming) or with oxygen (partial oxidation).

The reaction of steam reforming of gaseous methane

CH4+H2Aboutpairs.→CO+3H2

is endothermic, and it is usually performed at very high temperatures.

For the first operation of the reformer should enter the steam for assests the Deposit operations of the transformation with the change in the ratio of carbon monoxide and hydrogen (high and low), decarbonation by washing and subsequent purification of N2from the residual WITH by transformation WITH methane. At plants with more advanced technology after the first operation transformation with the change in the ratio of carbon monoxide and hydrogen (at high temperature) unit DGS (adsorption by pressure difference) allows you to directly separate the H2.

The efficiency and the value of investment in plant for H2mainly depends on the ratio of N2O/CH4temperature at the exit from the operation of the reformer (800-900°C)configuration section of the transformation with the change in the ratio of carbon monoxide and hydrogen, preheating of air and the efficiency of the unit AAA.

Direct partial oxidation of methane to synthesis gas

CH4+1/2 O2→CO+2H2

may also take place at moderate temperatures, but the reaction selectivity, which is difficult to control because of the presence of a complete combustion reaction, limits its industrial application.

Are now starting to be widely used method, which includes the combustion of methane to CO2and H2O simultaneously with the reaction of the reforming of CH4that is not reacted by N2And CO2(autothermal reforming), so esotericist one reaction uranova is foreseen by endothermically another. In the latter case, however, has the disadvantage of using pure oxygen for the combustion of methane, which requires a run of the subsidiary cryogenic unit for separating oxygen from air.

The number of sources that illustrate the above, very large, and here is the link to the introductory part of U.S. patent 4888131 as a list and summary of these materials.

It is known that the value of N2is the fact that this gas is used in the processing of oil hydrocracking, Hydrotreating)and in petroleum chemistry (synthesis Meon, DME, NH3, hydrocarbons using the Fischer-Tropsch synthesis).

The currently accepted method of reforming fuel and especially the strict technical requirements for product quality and sulfur content in diesel fuel will lead to an increasing demand for H2from oil refineries. In addition, there is also increasing interest in using hydrogen as the direction of energy, because of its potential characteristics as a "clean fuel", as it does not create harmful emissions and does not CO2.

Now, the Applicant has found advanced technology and feasible in industry solution for the production of high purity hydrogen from water and natural gas with conversion of carbon from the hydrocarbon is in essentially in CO 2in a stream with a high concentration, without inert ingredients.

A distinctive feature of this method is the production of gas in separate zones in order to avoid limiting the change of the ratio of carbon monoxide and hydrogen in the water gas thermodynamic equilibrium concentrations or the use of high temperatures for the conversion of methane, which in practice is seen as necessary conditions.

In fact, the subject of this invention relates to a method for producing hydrogen, which is based on application of redox solids, which when passing between the two reaction zones is restored in the presence of a suitable restorative flow, preferably hydrocarbon in one of these areas and again oxidized with a suitable agent to another of them with the formation of reduced forms oxidizing agent.

Another distinctive feature of the method according to this invention is the use of N2O and CO2as oxidizing agents for solids. This substance, in turn, is characterized by the fact that there may exist at least in two forms, more restored form and a more oxidized form, which differ widely depending on the oxygen content and the fact that it cycles through the reversible moves from more restored form to a more oxidized form.

Thus, according to this invention, hydrogen is produced by a method which includes the following operations:

a) oxidation of a solid substance in the first reaction zone;

b) the transition of the oxidized form solids in the reaction zone, which serves a restorative flow, and its reaction with the specified recovery flow;

c) removing the restored form solids and feed it into the first reaction zone;

d) the heat conducted preferably during one of the operations (b)or (C).

This method can also include other operations, depending on the degree of transformation and selectively participating reactions; thus, hydrogen is produced by a method which includes the following operations:

- oxidation of a solid substance in the first reaction zone; obtaining N2or, depending on the oxidizing compound;

- transition oxidized form solids in the subsequent reaction zone, in which the recovery of solids by means of its reaction with hydrocarbon;

- removing the restored form solids and submitting it to the subsequent reaction zone;

- supply of the gas phase obtained during the recovery of solids in the appropriate section of division, which allows baleari less complete separation of the products of complete combustion (CO 2and H2O) from any possible unreacted hydrocarbon and from any resulting by-products;

- possible recirculation of the above gas flow in the reaction zone in which there is a restoration of the oxide, and/or in the additional reaction zone for the complete conversion of the above-mentioned flow of products of complete combustion (CO2and H2O);

- remove from the series products of complete combustion (CO2and H2O)received from the cleaning sections.

While redox solid substance may be selected from a wide range of compounds, which will be described later in this invention, the oxidizing agent according to the method according to this invention may consist of N2O CO2or mixtures thereof; re-oxidation of a solid oxidizing agent can be spent in one transaction or through a series of operations, including, in addition to the above oxidizing agents, the use of O2, air or enriched air to at least one of these operations. If the oxidizing agent is not converted completely into the first reaction zone, the gas phase obtained in this reaction zone, you can send in the cooling system and separation with the separation and recycling of unreacted OK sausage agent in the same reaction zone.

Without going into the details of the mechanism of the various reactions involved in the process of this invention and, of course, without limiting its scope, it is possible to present a General schema transformations carried out by the above operations (together with various redox reactions), as follows, when considering the case when as oxidizing agents are used, respectively, N2O and CO2and above the reduction zone as hydrocarbon serves methane.

In the first case there is a direct production of hydrogen, while in the second case it is necessary to resort to traditional methods, which provide a simple and effective way of use for hydrogen production: for example, through one or more operations of the transformation with the change in the ratio of carbon monoxide and hydrogen

CO+H2O↔CO2+H2

with subsequent cleaning of H2in accordance with the above-described method.

In both cases 1) and 2) the process is endothermic and, therefore, for a process of producing hydrogen preferably, in addition to the three above-mentioned operations, to include interim operation of supplying the necessary heat.

Turning again, the number is about illustrative purposes, to the reaction schemes transformations, which presumably occur in separate reaction zones, the above scheme 1) and 2) can be visualized as the result of the following reactions:

in case of application of N2About as oxidizing agent and oxides and as redox solids:

Me represents an element and redox elements present in the solid, and x and y are correlated with valence and oxidation state of the Me, and x≥1 and≥0.

In the case of CO2as the oxidizing agent:

Me, x and y have the same meaning.

The transition form the oxidized solids from 3 to 4 or from 4 to 3 and from 5 to 6 or from 6 to 5), respectively, then spend through the appropriate supply of heat, which, therefore, is an essential operation of a process for producing hydrogen according to this invention: heat, thus, can be brought directly or indirectly, and the task of specialists in this field is to decide what specific procedure to apply, with any choice, of course, included in the scope of this invention.

Heat can be brought by burning part of the occasioned by hydrogen or by burning methane, natural gas or other hydrocarbons, or even through the use of heat, which is obtained by further oxidation of solid air.

As part or all of the heat can be summed predominantly in a separate reaction zone by burning more or less diluted molecular oxygen (O2products of incomplete combustion and possibly unreacted hydrocarbons present in the gas stream exiting the reaction zone, which is solid.

Again, based on their experience, experts in this field will be assumed to establish optimal conditions, and also in respect of reactions, based on the method of producing hydrogen according to this invention.

Solids that can be used are those substances which, including at least one element Me, are distinguished by the fact that the Me is selected from elements that have at least two States of oxidation stable under the reaction conditions, which differ in oxygen content in the sense that they are capable of cyclically move from more restored form to a more oxidized form and Vice versa.

You can use solids, containing one or more elements in the range from 20 to 80 wt.% by themselves or in mixtures with other items is nami, which does not undergo redox reactions; thus obtained reactive phase can, in turn, be used by itself or appropriately distributed in (or applied to) such compounds as silicon oxide, aluminum oxide or other pure oxides, such as oxides of magnesium, calcium, cerium, zirconium, titanium, lanthanum, and mixtures thereof.

Depending on the methods of obtaining and purification, through which they receive these oxides, in the case of cerium oxide or lanthanum usually present rare earth elements such as praseodymium and terbium, and in the case of the zirconium - hafnium. Some of these items that can be used as a carrier or dispersing phase, also undergo redox reactions; this applies, for example, cerium and praseodymium.

In the solid substance may also be present minor components called promoters or activators; they usually belong to the group of noble metals such as Pt, Pd, Au and Rh, preferably in amounts in the range from 0.01 to 2 wt.%, or, more to the transition metals, such as, for example, V, Cr, Mn, Ni, Nb, preferably in amounts in the range of from 0.1 to 15 wt.%.

Redox elements (Me), which may be present in the solid substance is, which should be used in the method according to this invention, preferably chosen from the group including CE, Pr, Ni, Fe, V, Mo, W in the form of salts, oxides or anhydrides.

These redox elements may be present in the form of binary compounds corresponding to the formula

where Me is one or more element selected from the group comprising of CE, Fe, W, Ni;

or in the form of compounds of the formula

where Me is one or more element selected from the group including CE, Pr, Co, Ni, Fe, Mo and W,

Z is one or more element selected from the group including CE, Zr, V and Mo; x≥1,≥0 and z≥1.

Of particular advantage is the use of solid substances containing as a main redox element Fe, preferably in amounts in the range from 20 to 60 wt.% Fe, in turn, is preferred in the described process, if it is present in the solid substance in the form of binary compounds together with a binary compound of cerium and/or ternary compounds corresponding to the formula (8), where Me=Fe, and Z=CE, specifically CeFeO3. Cr is particularly effective as element promoter in mixtures of binary or ternary compounds based on Fe and CE. The most widely used triple with the organisations with Me=Mo / Me=V is chosen from the group including CoMoO4, NiMoO4, Fe2(MoO4)3, (NiCo)MoO4, Cr2(MoO4)3, MnMoO4and CE2(YPA3)3, CoVOx, FeVOx, NiVOxand CrVOx.

The preferred configuration of the method involves feeding the H2In the first reaction zone (R1) to produce pure hydrogen. Obtaining CO2occurs in the second reaction zone (R2), and, consequently, the formation of these two types of gas are not limited by the equilibrium between the components of the water gas (WGS), which determines the overall technology steam reforming of natural gas. The flow coming from R2, consists of water and CO2, which, after separation from water by condensation is the only compound present in the output stream. Thus, if you want to produce hydrogen without allocation of CO2its removal is possible at much lower cost than in the case of steam reforming, where you should apply the changes in the ratio of carbon monoxide and hydrogen in the water gas and the Department of CO2by washing amines.

If the restore operation material gives, in addition to CO2and H2Oh, and SINCE H2you can enter the section separation to make the process more flexible. This section is division may use various well-known techno is Ogii, such as fractionated condensation, selective absorption of gas-liquid absorption physical and/or chemical type, selective absorption (gas - solid) with regeneration by changing the temperature or pressure (APT/TSA, DGS/PSA) and the use of membranes.

The availability section of the division has the following advantages:

- optional you should get a very high degree of conversion and selectivity in the burning of hydrocarbons in the second reaction zone, which, consequently, extends the range of redox solids that can be applied;

- it is possible to work the entire cycle in a relatively narrow temperature intervals and, therefore, limited by the problems of thermal exchange between the different zones, and the second reaction zone at a relatively moderate temperature levels.

This method is even more flexible in the sense that the recovery of the solids can be carried out with gases containing CO+H2from various sources. Thus, the section of the separation also allows you to use for this purpose, the gas discharged from the reactor R2, re-directing it in the same reactor after removal of CO2and H2O. This gas may also suitably be recycled to the reactor R3 and burn it there, to complement those of the economic balance. This thread can also be used as fuel to produce electrical energy by means of an appropriate system of gas turbine/generator of electricity or combustion/steam/steam turbine/generator of electricity.

The hydrocarbon, which is served in a reaction zone in which the recovered solid material may be selected from several species belonging to this group of compounds, with a special attention should be given to using aliphatic hydrocarbons, in particular methane and natural gas, even if for this purpose can be other suitable reducing agents, such as, for example, exhaust gases and chemical plants.

In the case when the oxidizing agent used CO2, Formed in the first reaction zone, can be used by itself for chemical applications, or it can be used to produce hydrogen through, as already mentioned, one or more operations of the transformation with the change in the ratio of carbon monoxide and hydrogen in the vapor phase.

In the scope of the present invention also includes the use in the first phase oxidation oxidizing agent consisting of a mixture of N2O and CO2; in this case the result is synthesis gas.

Section division may use different methods section is to be placed, such as fractionated condensation, selective absorption of gas-liquid, absorption, both physical and/or chemical type, selective adsorption (gas - solid) with regeneration under the influence of temperature or pressure (ARD, APT) and when using membranes.

Further details can be obtained by consideration of the following examples, which are given to better illustrate the present invention but in no way limit its scope.

Example 1

Referring to scheme 1, R1 and R2 respectively represent the first reaction zone (getting H2and the second reaction zone (reduction of the oxide by methane), while R3 represents an additional block to maintain the temperature where hydrogen is used as fuel (indirect heat).

In the first reaction zone (R1) serves water (line 1) and get H2(line 2). In the second reaction zone (R2) serves methane (line 3), and are formed combustion products: carbon dioxide and water (line 4). In an additional block (R3) maintaining the temperature of the served together hydrogen (line 5) and air (line 6); get (H2Oh, and nitrogen (line 7).

The scheme is complemented lines move substances that connect the three above-mentioned areas and move the recovered solid is facing R2, in optional block R3 temperature (line 9), the heated solid material in the reactor hydrogen (line 8), and oxidized solid - back in R2 (line 10).

In principle, the estimated response and the relative thermal effect of reaction can be estimated as follows (D.Stull, E.Westrum. Thermodynamics of organic compounds):

in R1 H2About⇒H2ΔH=241,8 kJ/mol (of 57.8 kcal/mol)
in R2 CH4⇒CO2+2H2AboutΔH=-801,9 kJ/mol (-191,7 kcal/mol)
in R3 1/2O2+H2⇒N2AboutΔH=-241,8 kJ/mol (-57,8 kcal/mol)
in R1 MeOx⇒MeO(x+1)ΔH=-4,H kJ/mol (-X kcal/mol)
in R2 MeO(x+1)⇒MeOHΔN=4,H kJ/mol (X kcal/mol),

where X is the characteristic associated with the chemical nature of the solid. Based on the known thermodynamic properties such as heat of formation of the oxidized phase and recovered phase in equilibrium with each other (Perry's Chem. Eng. Handbook), you can set the list of elements and the amount of heat associated with the redox reactions in which they participate; however, some of them are illustrative of the whole is mi in Table 1 below.

Table 1 gives the response related to the redox element contained in the solid, and the heat of formation of the two forms discussed under standard conditions: the oxidized form (DHox) and reduced forms (Dhred).

It is known that a more accurate determination of the heat absorbed/leased during the redox reaction of a rigid body must also include the amount of heat associated with the change of heat capacity of solids at constant pressure when the temperature changes that occur in the mass of the reagent; however, this last quantity of heat is usually small compared with the change of heat of formation determined at standard conditions, and therefore, DH°in Table 1, provides a reasonable approximation of thermodynamic characteristics of the material and, thus, can be used to calculate the mass and heat balance described below. You should specify, however, that this is only approaching thermodynamic characteristics of the material, if the element which forms the carrier or dispersing phase itself does not undergo redox reaction or no reaction with the restored and/or oxidized form of the redox element with the formation of other phases is whether compounds with relative allocation and/or absorption of heat of formation, which can be added to the heat of formation of redox element.

It should also be noted that the reactions are shown in Table 1, are theoretical and should be amended on the real factor shift the redox reaction with the used experimental conditions.

The possibility of experimental measurements of heat involved in the metabolism in redox reactions, the solids in the reaction conditions, which can be done by such devices as DSC (differential scanning calorimeter) or DTA (differential thermal analyzer), allows us to better determine the following balance sheet.

Table 1
The oxidized formThe reduced formDHox"J/mol (kcal/mol)DHredkJ/mol (kcal/mol)DH°kJ/mol (kcal/mol)
And 2CeO2=CE2O3+0.5o2-1037,0

(-247,9)
-1819,2

(-434,9)
254,7

(60,9)
F 1Fe2O3=2FeO+0.5o2-822,0

(-196,5)
-264,8

(-63,3)
292,4

(69,9)
G 1Fe3O4=3Fe+2O2-1111,8

(-265,8)
0(0)1111,8

(265,8)
N 1Fe3O4=3F+0.5o2-1111,8

(-265,8)
-815,7

(-195)
296,2

(70,8)
I Moo3=1MoO2+0.5o2-745,0

(-178,1)
-589,0

(-140,8)
156,0

(37,3)
L 1NiO=1Ni+0.5o2-239,7

(-57,3)
0(0)239,7

(57,3)
M Rho2=1Pr2O3+0.5o2-961,7

(-229,9)
-1822,5

(-435,7)
100,8

(24,1)
P 1V2O5=1V2O3+1O2-1551,5

(-370,9)
-1218,5

(-291,3)
333,0

(79,6)
Q 1WO3=1WO2+0.5o2-842,5

(-201,4)
-589,4

(-140,9)
253,1

(60,5)

Thus, it is possible to set the mass/heat balance in relation to Figure 1, which, assuming the justice of all the above assumptions and all individual transaction differs 100% efficiency and can be self-consistently from a thermal point of view by equating indeterminist the reaction zones 1 and 2 for block temperature.

For the balance of mass, are shown in table 2 with respect to the main components, as the basis for calculation, it was assumed that produces 50 t/h of hydrogen (line 2) when using an item that has thermodynamic properties that are listed in row 1 of Table 1 and assuming that this oxide is deposited on a substrate, comprising 50 wt.%.

Table 2
Line12345678910
t/ht/ht/ht/ht/ht/ht/ht/ht/ht/h
H2508,5
H2About45022576,9
CO2275#x0200A;
CO
M32003200
MO3600
N2222,4222,4
O268,3
CH4100
Media320032003200
Total450501005008,5290,7299,3640064006800

From the data presented in Table 2, we can see that you can get from 100 t/h of methane, a net production of hydrogen is 41.5 t/h (at 100% purity). 41,5 t/h H2provided by getting 50 t/h in the reaction zone 1 and the consumption of 8.5 t/h block to maintain the temperature; at the same time, the formation of a concentrated stream of CO2and H2O without inert ingredients, which is 500 t/h, with recirculation 6400-6800 t/h of solids between the two reaction zones.

Thus, it should be noted that the predominant aspect of the proposed method is to obtain gases in the recovery of solids (CO2and H2O) and obtain H2in separate zones, which significantly reduces the cost of separation and purification of hydrogen.

If thermodynamic characteristics of solids are known, we can estimate thermal levels of the two react the local areas. Table 3 below indicates the temperature relating to the lines 8, 9 and 10, calculated for several values of DH°. These calculations were carried out without taking into account (in first approximation) tangible heat of the gas flow and by attributing heat transfer in the system only the motion of a rigid substance, which is characterized by the specific heat capacity (CP), equal to 1.05 j/g/°With(0.25 cal/g/°). In the situation described, due to the mass effect of the heat transfer solid substance prevails over heat associated with gas flows; furthermore, the sensible heat of the gas streams can be extracted by appropriate heat exchange between incoming and outgoing flows of the two reaction zones.

Table 3
DH° kJ/mol (kcal/mol)Line 8 (°)Line 9 (°)Line 10 (°)
And154,8(37)700565399
Inof 234.2 (56)700657691
255,2(61)600539618
D292,8 (70)600443778

You can see that amended the application of heat on solid matter the temperature profile of the two reaction zones is changed, reaching, for example, assuming use of the element with thermodynamic characteristics are shown in Table 3, line In, essentially flat profile.

It should also specify that the temperature cycle of hydrogen production are generally lower than the temperature which is generally used in the existing methods of hydrogen production by steam reforming or autothermal reforming of methane, and this is another predominant aspect of the proposed method.

Example 2

In relation to the scheme shown in Figure 2, R1 and R2 respectively represent the first reaction zone (getting H2and the second reaction zone (reduction of the oxide by methane), while R3 represents an additional unit of temperature in which used fuel is methane as an alternative to hydrogen.

In the first reaction zone (R1) is water (line 1) and get the H2(line 2), Methane (line 3) served in the second reaction zone (R2), and produces combustion products: carbon dioxide and water (line 4). Methane (line 5) and air (line 6) jointly enter into an additional block (R3) maintain the temperature, and the obtained N2O, carbon dioxide and nitrogen (line 7).

The scheme is complemented lines of migration of substances that connect the three above-outie zone and move the recovered solid, coming out R2 in the reactor hydrogen (line 10), and oxidized solid material in the additional block R3 temperature (line 9) and heated solid material back to the reactor R2 (line 8).

Under the same assumptions as in example 1 production of 50 t/h (line 2) requires 121 t/h of methane, which is distributed between the response and recovery (line 3) and temperature (line 5). From reactor R2 enters the flow 500 t/h, consisting of CO2and H2O. Solid substance has a content capable of reversible exchange of oxygen of about 6 wt.%. The composition of the various streams is given in Table 4. Temperature output streams are 534° (line 8), 399° (line 9) and 700° (line 10), respectively.

Example 3

When considering the flowchart shown in figure 2, R1 and R2 represent, respectively, the first reaction zone (receive FROM) and the second reaction zone (reduction of the oxide by methane), while R3 represents an additional unit of temperature in which methane is used as fuel.

CO2(line 1) enters the first reaction zone (R1)and is obtained FROM (line 2). Methane (line 3) served in the second reaction zone (R2), and produces combustion products: CO2and H2On (line 4). Methane (line 5) and air (line 6) served together in to ornately block (R3) temperature, and get H2Oh, carbon dioxide and nitrogen (line 7).

To calculate the composition of the various streams were assumed receipt of 140 t/h of carbon monoxide, from which you can get about returns 112,000 Nm3hydrogen using conventional methods.

Taking the same assumptions as in example 1, for a specified production requires about 28 t/h of methane. Solid is the content capable of reversible exchange of oxygen of about 6% wt.

Example 4

When considering the flowchart shown in figure 2, R1 and R2 represent, respectively, the first reaction zone (receipt N2and the second reaction zone (reduction of the oxide by methane), while R3 represents an additional unit of temperature in which hydrogen is used as fuel.

Water is fed (line 1) in the first reaction zone (R1) and get H2(line 2). Methane is served (line 3) to the second reaction zone (R2) and receive combustion products: carbon dioxide and water (line 4). Hydrogen (line 5) and air (line 6) served together in the additional block (R3) maintaining the temperature regime and get H2O and nitrogen (line 7).

To calculate the composition of the various streams involve the production of hydrogen 150000 Nm3/h 13.4 t/h of Solid substance has a content capable of reversible exchange of color is Yes about 6 wt.%.

The consumption of methane to obtain in pure form 124373 Nm3/h of hydrogen is 37500 Nm3/h, of which 25627 Nm3/h send in the block temperature. The composition of the flows is given in Table 4.

In the case of the proposed scheme specific consumption of methane, measured in energy per volume of N2as well 10,71 GJ (2,56 Gcal) to obtain pure 1000 Nm3H2when using the value of the calorific value of methane is less 35555,5 kJ/Nm3(8500 kcal/Nm3); in addition, the specific allocation of CO2is approximately 300 Nm3at 1000 Nm3received N2. The last value represents a preferred aspect of this method from the standpoint of effectiveness in protecting the environment, as it will significantly below normal values, for selection of CO2in the environment for other known methods of obtaining the H2. For example, steam reforming of methane is characterized by the specific emissions of CO2that is usually more than 360 Nm3at 1000 Nm3H2(Modern Production Technologies in 1997 Nitrogen CRU Publishing Ltd, p.102-115).

9
Table 4
Line1234567810
Nm3/hNm3/hNm3/hNm3/hNm3/hNm3/hNm3/ht/ht/ht/h
H215000025627
H2O1500007500025627
CO237500
CO
M857
MO964964
N24765447654
O212814
CH437500
Media857857857
Total15000015000037500112500256276046873281182118211714

Example 5 (comparative)

The following table 5 indicates the energy consumption for different the x configuration method, associated with the production of hydrogen in steam reforming of natural gas that can be applied to plants with a production of H2to 566000 Nm3/h; moreover, the data include the energy consumption when using natural gas as fuel and raw materials (food) and are indicated for the three configurations typical methods of Modern Production Technologies in 1997 Nitrogen CRU Publishing Ltd, p.102-115), where the base case is characterized by the outlet temperature of the reforming-850 installation°C, ratio of steam to carbon of 3.2 and effectiveness of ARD 86%. From the given data one can see that the predominant characteristic in the present invention method is the specific energy consumption of natural gas, equal 10,71 GJ/Nm3(2,56 Gcal/1000 Nm3) H2(specified in example 4), which is lower than typical values for process steam reforming, are given in Table 5.

Table 5
Consumption at 1000 Nm3H2The basic versionBasic options-t + nicotinuric. transformation with changing aspect]. CO and H2Base case+pre-reforming-set
Food GJ(Gcal)13,2(3,15)12,6(3,02)13,2(3,15)
Fuel GJ (Gcal)3,39(0,81)4,06 (0,97)2,97(0,71)
Food+fuel GJ(Gcal)16,6(3,96)16,69(3,99)16,10(3,85)

Example 6

Part of the solids, containing 61% Fe2About3and 39% SEO2(1732) after oxidation in air at 800°subjected under conditions of thermal equilibrium cycle recovery 100% methane in isothermal temperature conditions at 780°C. the Obtained dependence compared with dependencies related to the quantities of other solid substances with the same content of Fe2About3but with 39% of Al2O3, SiO2, MgO and ZrO2respectively.

This comparison is shown in Fig 3, which shows the weight loss (due to oxygen evolution) depending on the time of the experience. The oxidized sample was washed by a stream of nitrogen for 102,5 minutes, after which the stream is directed at the sample was replaced with nitrogen on methane.

The results obtained demonstrate that the solid substance that contains SEO2under certain conditions reacts with methane to more quickly and more effectively than a solid substance containing other dispersing agents for iron oxide.

Example 7

6.6 g of a solid substance containing 61% Fe2About3and 39% SEO2have loaded in microreactor the fixed bed at 750° C and atmospheric pressure, at an average hourly rate of gas supply, equal to 150. This solid was subjected to the following experiment:

oxidation in air at 750°, hourly average gas flow rate=150, time=60 min; purge stream of nitrogen;

restoration of methane at 100%, 750°and With an average hourly rate of gas supply=150 for 60 min;

blowing a stream of nitrogen;

oxidation of nitrogen saturated with water at 80°With, at 750°C for 120 min;

restoration of methane at 100%, 750°and With an average hourly rate of gas supply=150 for 20 min;

measurement of the degree of conversion of methane to 19%.

Example 8

Solid, containing 61% Fe2About3, 5% Cr2O3the rest - CEO3(1786), was subjected to the same experience as solid in example 7, having a degree of conversion of methane to 26%.

Cr makes a material based on iron and cerium in the promoter of combustion of methane.

Example 9

7.5 g of a solid substance containing 50 wt.% CoMoO4(the rest is CeO2), after calcination in muffle at 800°loaded into a microreactor with a fixed layer and subjected to a cycle of methane recovery at 100%, 750°With an average hourly rate of gas supply=150, (and the composition of the reaction products was measured during flow through gas chromatographic analysis). After about 260 minutes reacts and the degree of conversion of methane was 22.5%; and it was found that the output stream consists of CO2- 6,5% vol., CO - 8,9% vol., H2On - 12,0% vol., H2- 18,7% vol., the rest was unreacted methane. At the end of the feed methane solid was rinsed with nitrogen for about 60 minutes to remove residual traces of methane and reaction products, and then, at the same temperature 750°S, it was washed by a stream of nitrogen 30 ml/min, before entering the reactor passed through a saturator water, supported at the temperature of 90°C. In the effluent from the reactor flow detected the presence of H2. The number of N2selected from H2Oh, produces oxidation of solid, which corresponds to 1.7 wt.% oxygen, acquired a solid.

Example 10

When considering the scheme in figure 4, R1 and R2 respectively represent the first reaction zone (getting H2and the second reaction zone (reduction of the oxide by methane), R3 represents an additional for the preceding zones block (heat generator), while the SS1 is a section of the separation.

In the first reaction zone (R1) serves water (line 1) and get H2(line 2). In the second reaction zone (R2) serves methane (line 3), and as the combustion products are formed CO3H2O, CO and N2(line 4). This thread serves in section SS1 sec the population, from which the discharge flows consisting of H2On (line 4A), and CO2(line 4b), and the flow of CH4+WITH+H2(line 4C1) extract and distribute area R3 maintain the temperature above the reactor R2 (line 4 C1/1 and line 4C1/2, respectively). Air (line 6) put in the same block R3 together with the above-mentioned flow of CH4+WITH+H2getting H2O CO2and nitrogen (line 7). This scheme complements the lines of the transfer of a substance, which connect the above three areas, and which can move oxidized solid material leaving zone R1, additional block R3 temperature (line 9), the heated solid material, leaving the zone - in area R2 recovery (line 8), and the recovered solid is discharged from it back into the reactor for producing hydrogen (line 10).

Section SS1 is, in particular, from (figa):

a) partial condenser (E1), which allows you to remove the water (line 4A), obtained when the restore operation is conducted in R2;

(b) membrane separation unit (M1), which allows you to remove CO2(line 4b) and extract stream comprising CO, H2and CH2present in the stream exiting the R2 (line 4C); this section does not include equipment AD1 and output lines required to work in conditions of industrial enterprises.

Anticipated reactions, the relative thermal effect of reaction, heat of formation of oxidized and reduced phases in equilibrium with each other and other properties of the considered compounds can be estimated as follows (thermodynamics of Organic Compounds/ Thermodynamics of organic compounds - D.Stull, E.Westrum):

in R1 H2O⇒H2+1/2O2ΔH=241,8 kJ/mol (of 57.8 kcal/mol)
in R2CH4+2O2⇒CO2+2H2OΔH=-801,9 kJ/mol (-191,7 kcal/mol)
in R3 1/2O2+H2O⇒H20ΔH=-241,8 kJ/mol (-57,8 kcal/mol)
in R3 CH4⇒CO2+2H2OΔH=-801,9 kJ/mol (-191,7 kcal/mol)
in R3 WITH+1/2O2⇒CO2ΔH=-282,8 kJ/mol (-67,6 kcal/mol)
in R1 MeOx+1/2O2⇒MeO(x+1)ΔN=-X kcal/ mol
in R2 MeO(x+1)⇒MeOx+1/2O2ΔH=X kcal/mol,

where X is a characteristic associated with the chemical nature of the solid.

Thus, it is possible to set the mass/heat balance (see Figure 4/4A), which may be from a thermal point of view, self-consistent, by equating the total is indeterminate reaction zones 1 and 2 for block temperature 3, demonstrating that section SS1 does not require heat.

The attached table 6 contains the balance by weight, with respect to the major components; where as the basis for calculation was made getting 100000 Nm3/h of hydrogen when using iron oxides, thermodynamic properties that are listed in rows E and F of Table 1, assuming that the oxide deposited on a 40 wt.% media (typically cerium oxide).

It should be noted that the separation of the greater part of the water present in the stream exiting the reactor R1 (line 2), shall be implemented by one of the traditional cooling systems with successive/simultaneous separation of the gas phase (specifically line 2A: N2) from the liquid phase (specifically, line 2b: H2O), obtained upon cooling; this complex is not specified on Figure 4 above.

You should also take note that a small amount of water present in the stream exiting the R2 also separated after cooling and subsequent operations on the separation of gas and liquid phases, which is carried out on line 4C, emerging from the M1, after separation of the CO2. Figa not illustrate these operations; in table 2 the column 4A refers to water flow, slightly separated in the condenser E1, and the column 4A' refers to water flow, separate action on line 4C. This process is carried out at 20 kg/cm2.

If thermodynamic characteristics of the solid substance in question, known, we can estimate the temperature levels of the three reaction zones. The following table lists the calculated temperature related to lines 8, 9 and 10:

a) R1⇒680°C

b) R2⇒848°

c) R3⇒735°C.

It is also worth noting that the temperature of the production cycle in General lower than the temperature of, usually used in existing processes for hydrogen production by steam reforming or autothermal reforming of methane, and it is the predominant aspect of the proposed method.

Figure 5 represents another working scheme in relation to the previous described and shown on Figure 1, where the reaction zone R3 temperature is in the processing chain after R2: solid material emerging from R3, served in R1.

Example 11

Solid substance containing 80 wt.% Fe2About3(the rest is ZrO2), obtained by joint precipitation was then impregnated with an aqueous solution containing dichlorodiammineplatinum to obtain a composition containing 0.1 wt.% Pt.

After firing in a muffle at 800°, 8 grams of solids were granulated loaded in the micro-reactor with a fixed bed and subjected to a cycle of methane recovery at 100%,750° With an average hourly rate of gas supply=150, and the composition of the exit stream was measured during flow by gas chromatography analysis. After about 10 minutes the reaction of methane reacted at 100%, and the output stream consisted of CO2and H2About with small amounts of CO/H2. After about 30 minutes the reaction was reacted with 60% methane; after 60 minutes, the degree of conversion amounted to over 80%.

The introduction of Pt increases the reaction rate of combustion of methane. This becomes especially obvious when comparing the values of the degree of conversion of the material, the modified Pt, with the degree of conversion obtained in the same conditions in example 7.

Table 6
Line1 (mol/h)OBS. (mol/h)2A (mol/h)2b (mol/h)3+4 S1/2 (mol/h)4C1/2 (mol/h)3 (mol/h)
H24461,504461,501414,341414,34
H2About5533,80892,3016,74875,568,648,64
CO2&x0200A; of 46.68of 46.68
CO707,17707,17
M
MO
N2
O2
CH42031,44157,071874,36
media
Total (t/h)964492506992961577357460,02739030070

Prodoljeniyami 6

Line4 (mol/h)4A (mol/h)4A' (mol/h)4A+4A' (mol/h)4b (mol/h)4C1 (mol/h)4C1/1 (mol/h)
H21828,501828,50414,16
H2O3251,153233,966,033239,9911,162,53
CO21667,881607,5360.3513,67
CO914,25914,25207,08
M
MO
N2
About 2
CH4203,07203,0746,00
media
Total t/h16453158,2601095836970747354108020

Continuation of table 6

Line4C1/2 (mol/h)5 (mol/h)6

(mol/h)
7 (mol/h)8 (mol/h)9 (mol/h)10 (mol/h)
H21414,34
H2About8.64508,68
CO2of 46.68266,74
CO707,17
M
MO
N26577,946577,94
About21248,5723058
CH4157,07
media23318,0323318,0323318,03
Total (t/h)27390240220212550360477635690863497706

1. The method of producing hydrogen and carbon dioxide, characterized in that h is about it includes the following operations:

a) oxidation of a solid substance in a first reaction zone with hydrogen production;

b) the transition of the oxidized form of a solid substance to another reaction zone, which serves the flow of reducing agent selected from hydrocarbons, and its reaction with a stream of reducing agent to obtain carbon dioxide;

c) removing the restored form solids and feed it into the first reaction zone;

d) carry out the heat with the help of an additional unit of the temperature control, located between the two reaction zones, with the use of heat, which is obtained by further oxidation of solid air.

2. The method of producing hydrogen according to claim 1, where the heat carried out preferably during one of two operations: (b) or (C).

3. The method of producing hydrogen according to claim 1, characterized in that the solid substance in the first reaction zone reacts with an agent selected from the group comprising H2O and mixtures thereof with CO2.

4. The method of producing hydrogen according to claim 3, characterized in that the solid substance in the first reaction zone preferably reacts with H2O.

5. The method of producing hydrogen according to claim 1, characterized in that the solid substance which is subjected to oxidation in the first reaction zone includes at least one cell battery (included) is t, characterized by at least two different oxidation States, which are stable at the reaction conditions.

6. The method of producing hydrogen according to claim 5, characterized in that it is solid, in two different situations, additionally characterized by different amounts of oxygen and enthalpy and capable of cyclically and continuously move from the restored form to the oxidized form and Vice versa.

7. The method of producing hydrogen according to claim 6, in which the solid substance is present in at least one redox element in the form of binary compounds corresponding to the formula

IUxAbouty,

where Me is selected from the group including CE, Fe, W, Ni;

or in the form of compounds of the formula

IUxZzOy,

where Me is one or more element selected from the group including CE, Pr, Co, Ni, Fe, Mo and W, a Z is one or more element selected from the group including CE, Zr, V and Mo; x≥1,≥1 and z≥1.

8. The method of producing hydrogen according to claim 7, where Me represents Fe.

9. The method of claim 8, where the iron is present in the solid substance in a quantity in the range from 20 to 60 wt.%.

10. The method of producing hydrogen according to claim 9, where Fe is present in the solid substance in the form of binary compounds together with a binary compound of cerium and/or connect the tions, corresponding to the formula (8), where Me=Fe, and Z=Ce.

11. The method of producing hydrogen according to claim 10 where the compound corresponding to the formula (8)is CeFeO3.

12. The method of producing hydrogen according to at least one of p-11, where the solid also contains as a promoter metal selected from the group comprising Pt, Pd, Au and Rh.

13. The method according to item 12, where the promoter is contained in a percentage in the range of from 0.01 to 2 wt.%.

14. The method of producing hydrogen according to at least one of p-11, where the solid also contains as a promoter is a transition metal selected from the group including Cr, Mn, Nb, and V.

15. The method according to 14, where the promoter is contained in an amount in the range of from 0.1 to 15 wt.%.

16. The method of producing hydrogen according to item 15, where the promoter is present in chrome.

17. The method of producing hydrogen according to claim 7, where the reactive phase, thus obtained, in turn, can be used as such or appropriately distributed or caused by compounds such as silicon oxide, aluminum oxide or other pure oxides, such as oxides of magnesium, calcium, cerium, zirconium, titanium, lanthanum, and mixtures thereof.

18. The method of producing hydrogen by 17, where the reactive phase is present in an amount in the range of from 20 to 80 wt.% in relation to the connection, which is the OE forms a carrier or dispersing phase.

19. The method of producing hydrogen according to claim 1, characterized in that the hydrocarbons are selected from aliphatic hydrocarbons.

20. The method of producing hydrogen according to claim 19, where the aliphatic hydrocarbon is CH4or natural gas.

21. The method of producing hydrogen according to claim 1, where the heat is carried out, using as fuel hydrogen.

22. The method of producing hydrogen according to claim 1, where the heat carried out using methane as fuel, or natural gas.

23. The method of producing hydrogen according to claim 1, characterized in that it comprises the following operations:

oxidation of a solid substance in a first reaction zone with obtaining H2;

the transition of the oxidized form of the solid in the following reaction zone, in which the recovery of solids by reaction with hydrocarbon;

removing the restored form solids and feeds it into a subsequent reaction zone;

the flow of the gas phase obtained in the recovery of solids in the appropriate section of division that allows more or less completely to separate the products of complete combustion (CO2and H2O) from any possible unreacted hydrocarbon and from any resulting by-products;

possible recycling of the above vasovasotomy in the reaction zone, where the recovery of oxide, and/or in the additional reaction zone, to enable the above thread to turn into the products of complete combustion (CO2and H2About);

remove from the series products of complete combustion (CO2and H2On emerging from the cleaning sections.

24. The method of producing hydrogen according to claim 1, where the heat is carried out by combustion of part of the formed hydrogen or by burning methane or other hydrocarbons.

25. The method of producing hydrogen according to claim 1, where the heat is carried out by use of heat, which is obtained by further oxidation of solid air.

26. The method according to item 21, where water is served (1) in the first reaction zone (R1) and get H2(2)in the second reaction zone (R2) submit (3) methane and receive combustion products: carbon dioxide and water (4); hydrogen or methane (5) and air (6) served together in the additional block (R3) maintaining the temperature, thus get H2Oh, nitrogen and, if joint filing of methane, carbon dioxide (7), and these three areas are connected by lines move, in which the recovered solid material, leaving the second reaction zone (R2), guide (9) additional block (R3) maintaining the temperature of the heated solid guide (8) in the first reaction zone (R1), and Oka is certain solid guide (10) back into the second reaction zone (R2).

27. The method according to claim 1, where the water is served (1) in the first reaction zone (R1) and get H2(2)in the second reaction zone (R2) served (line 3) methane and receive combustion products: carbon dioxide and water (line 4); the hydrogen or methane (5) and air (6) served together in the additional block (R3) maintaining the temperature, thus get H2Oh, nitrogen and, if joint filing of methane, carbon dioxide (7), and these three areas are connected by lines move, in which the recovered solid material, leaving the second reaction zone (R2), send (10) in the first reaction zone (R1)and oxidized solid guide (9) additional block (R3) maintain the temperature, and the heated solid guide (8) back into the second reaction zone(R2).

28. The method according to claim 1, where CO2served (1) in the first reaction zone (R1) and receive (2), the second reaction zone (R2) submit (3) methane and receive combustion products: CO2and H2About (4); hydrogen or methane (5) and air (6) served together in the additional block (R3) maintaining the temperature, thus get H2Oh, nitrogen and, if joint filing of methane, carbon dioxide (7), and these three areas are connected by lines move, in which the recovered solid material, leaving the second reaction zone (R2), guide (9) additional block (R3) support the of temperature, the heated solid guide (8) in the first reaction zone (R1)and oxidized solid guide (10) back into the second reaction zone (R2).

29. The method according to claim 1, where CO2served (1) in the first reaction zone (R1) and receive (2), the second reaction zone (R2) submit (3) methane and receive combustion products: CO2and H2About (4); hydrogen or methane (5) and air (6) served together in the additional block (R3) maintaining the temperature, thus get H2Oh, nitrogen and, if joint filing of methane, carbon dioxide (7), and these three areas are connected by lines move, in which the recovered solid material, leaving the second reaction zone (R2), send (10) in the first reaction zone (R1), oxidized solid guide (9) additional block (R3) maintain the temperature, and the heated solid guide (8) back into the second reaction zone (R2).

Priority items:

21.12.2000 according to claims 1 to 29.



 

Same patents:

FIELD: production of gas mixture containing hydrogen and carbon oxide from hydrocarbon raw material.

SUBSTANCE: proposed method includes the following stages: (a) partial oxidation of part of raw material for obtaining the first gaseous mixture from hydrogen and carbon oxide; (b) catalytic vapor reforming of part of gaseous raw material in convective vapor reforming furnace provided with tubular reactor with one or more tubes containing reforming catalyst. Outer surface of tubular reactor tubes is used for cooling the hot gas obtained at stage (a). Surface of these tubes is made from metal alloy containing 0-20 mass-% of iron, 1-5 mass-% of silicon, 0-5 mass-% of aluminum, 20-50 mass-% of chromium and at least 35 mass-% of nickel.

EFFECT: reduction of coke formation and erosion of outer surfaces of reactor tubes.

11 cl

FIELD: technology of processing hydrocarbon materials, production of synthesis-gas in particular.

SUBSTANCE: proposed method is carried out in plant including multi-cylinder four-stroke or two-piston air-injection internal combustion engine working in mode of chemical compression reactor. Proposed method consists in preparation of mixture containing hydrocarbon material, water vapor and oxygen-enriched air -fuel charge at excess-air-oxidizer coefficient of 0.3-0.58 for methane followed by preheating of fuel charge and delivery of it to engine cylinders; then additional heating is performed in compression stroke followed by ignition in top dead center due to self-ignition of additives introduced into fuel charge in form of liquid or gaseous agents whose ignition temperature is below that of fuel charge; as a result, engine is started as chemical compression reactor and partial oxidation of fuel in volume of internal combustion cylinders is performed; then, products formed during reverse stroke of piston are expanded and cooled and products of this process containing synthesis-gas are discharged to bottom dead center, after which they are cooled and cleaned from soot and are subjected to final cooling and conversion into methanol or dimethyl ether. Process of partial oxidation at attaining the working mode of operation by chemical reactor is maintained due to availability of residual gases in cylinders whose amount is controlled by re-adjusting of the valve gear, additional heating due to warming-up of engine and external control of fuel charge heating temperature. Proposed plant includes multi-cylinder four-stroke or two-piston two-stroke air-injection internal combustion engine working as chemical compression reactor; engine is provided with intake and exhaust valves and system for delivery of air, hydrocarbon material and additives, as well as heating and preheating systems including air heaters, heat exchangers and mixer; engine is also provided with synthesis-gas cooling system which also consists of heat exchanger and cooler; engine is provided with reversible motor-generator set generating the electric power for multi-stage synthesis-gas compressor and high-temperature filter rigidly connected with engine and used for cleaning the synthesis-gas from soot; engine is provided with cooler and drip pan. Working of engine in mode of chemical compression reactor and composition of synthesis-gas are controlled through control of oxidizer-excess coefficient and preheating temperature in heat exchanger at steady state conditions or temperature at starting air heater outlet. Invention makes it possible to increase specified productivity by 2.5-3 times at volume ratio of H2/CO of 1.4:2.

EFFECT: enhanced efficiency of production of methanol and synthetic motor fuels.

2 cl, 1 dwg, 1 tbl

FIELD: petrochemical processes.

SUBSTANCE: process of producing benzene, ethylene, and synthesis gas from methane comprises following stages: (i) supplying into reactor initial gas containing methane and carbon dioxide; (ii) oxidation of methane in reactor under specific reaction conditions using first catalytic material and/or additional oxidant; and (iii) removal from reactor of gas stream formed containing benzene, ethylene, and synthesis gas, inside wall of reactor having been treated with first catalytic material.

EFFECT: increased conversion of methane and selectivity regarding benzene at reduced accumulation of coke fragments.

20 cl, 9 tbl, 9 ex

FIELD: petrochemical processes.

SUBSTANCE: process of producing benzene, ethylene, and synthesis gas from methane comprises following stages: (i) supplying into reactor initial gas containing methane and carbon dioxide; (ii) oxidation of methane in reactor under specific reaction conditions using first catalytic material and/or additional oxidant; and (iii) removal from reactor of gas stream formed containing benzene, ethylene, and synthesis gas, inside wall of reactor having been treated with first catalytic material.

EFFECT: increased conversion of methane and selectivity regarding benzene at reduced accumulation of coke fragments.

20 cl, 9 tbl, 9 ex

FIELD: chemical industry; chemical reactor and the method for production of hydrogen.

SUBSTANCE: the invention is pertaining to the power equipment may be used for production of hydrogen both in the stationary plants and on the vehicles. The hydrogen is produced by the hydrolysis (decomposing of water) at its interaction with the granules of the solid reactant (aluminum, silicon, etc.) definitely located inside the chemical reactor. The chemical reactor for production of the hydrogen consists of the cylindrical body with the liquid reactant medium, in which there is the temperature sensor connected with the control unit, and in the upper part of the body there is the union for withdrawal of the gaseous product of the reaction. At that inside of the body the tubular heat exchanger is installed. The tubes of the heat exchanger are arranged at least along two concentric circumferences, spaced from each other and communicate through the collector equipped with the valves for feeding of the heating carrier. Between the tubes of the heat exchanger in the liquid reactant medium there is the annular fire grate, on which the solid reactant granules are placed. The chemical reactor has the vertical spacers inserted between the tubes located on the concentric circumferences shutting the gap between the adjacent tubes. Besides there are the vertical inserts placed between the opposite tubes of the adjacent concentric circumferences shutting the gap between the tubes. At that the indicated spacers and inserts form the zones free from the solid reactant granules, and the valves of the heat carrier feeding are connected through the control unit to the temperature sensors. The method of operation of the chemical reactor for production of hydrogen provides for the liquid reactant feeding in the chemical reactor, withdrawal of the heat and the reaction products from the reaction zone with the help of the heat carrier. Before the liquid reactant feeding into the chemical reactor this reactant is heated up to the temperature ensuring the preset duration of the operational cycle of the reaction, and the heat withdrawal from the chemical reactor with the help of the heat carrier begin at reaching the temperature equal to the temperature of the liquid reactant boiling point with the increase of the heating carrier consumption till the boiling temperature of the liquid reactant will drop to 0.9÷0.8 of the liquid reactant boiling temperature, after that the consumption of the cooling heat-carrier maintain constant till completion of the chemical reaction in the chemical reactor. The inventions allow to increase efficiency of the chemical reactor, to reduce its dimensions and the mass, to improve the fire-explosion safety, to simplify the chemical reactor operation, to reduce its operational costs.

EFFECT: the inventions ensure the increased efficiency of the chemical reactor, the reduced its dimensions and the mass, the improved the fire-explosion safety, the simplified operation of the chemical reactor, the decreased its operational costs.

2 cl, 1 dwg

FIELD: separation and cleaning of synthesis-gas.

SUBSTANCE: proposed section consists of device for partial condensation of synthesis-gas including the following components: heat exchanger A for cooling the synthesis-gas fed to section, separator B connected with heat exchanger A and intended for separation of synthesis-gas into gas fraction consisting mainly of hydrogen and carbon monoxide and liquid fraction consisting mainly of carbon monoxide and methane, evaporator C for further separation of gas fraction fed from separator B into gas fraction consisting mainly of hydrogen and liquid fraction consisting mainly of carbon monoxide, evaporator D where hydrogen absorbed in liquid and remaining liquid containing mainly carbon monoxide are evaporated; this liquid may be directed to distilling tower; section is also provided with one more evaporator E where hydrogen absorbed in liquid fraction of separator B is removed through evaporation; this liquid contains mainly carbon monoxide and methane; liquid may be directed to distilling tower F for separation of gaseous carbon monoxide and obtaining methane from lower part of column. Section is also provided with unit for washing with nitrogen which includes washing column G for separation of admixtures by action of nitrogen from gas fraction of evaporator C and recovery of admixtures as fuel gas. Nitrogen washing unit adjoins the partial condensation device.

EFFECT: enhanced heat exchange; low cost of process.

13 cl, 1 dwg, 1 tbl

FIELD: separation and cleaning of synthesis-gas.

SUBSTANCE: proposed section consists of device for partial condensation of synthesis-gas including the following components: heat exchanger A for cooling the synthesis-gas fed to section, separator B connected with heat exchanger A and intended for separation of synthesis-gas into gas fraction consisting mainly of hydrogen and carbon monoxide and liquid fraction consisting mainly of carbon monoxide and methane, evaporator C for further separation of gas fraction fed from separator B into gas fraction consisting mainly of hydrogen and liquid fraction consisting mainly of carbon monoxide, evaporator D where hydrogen absorbed in liquid and remaining liquid containing mainly carbon monoxide are evaporated; this liquid may be directed to distilling tower; section is also provided with one more evaporator E where hydrogen absorbed in liquid fraction of separator B is removed through evaporation; this liquid contains mainly carbon monoxide and methane; liquid may be directed to distilling tower F for separation of gaseous carbon monoxide and obtaining methane from lower part of column. Section is also provided with unit for washing with nitrogen which includes washing column G for separation of admixtures by action of nitrogen from gas fraction of evaporator C and recovery of admixtures as fuel gas. Nitrogen washing unit adjoins the partial condensation device.

EFFECT: enhanced heat exchange; low cost of process.

13 cl, 1 dwg, 1 tbl

Catalytic reactor // 2296003

FIELD: chemical industry; production of the catalytic reactors.

SUBSTANCE: the invention is pertaining to the chemical industry, in particular, the catalytic reactor, which contains a set of the sheets forming the channels of the streams between them. In each channel of a stream there is the wavy material foils, which surfaces are coated with the catalytic material, except for the places where they contact to the sheets. On each end of the reactor there are the gas-collecting mains for the gaseous mixtures feeding in the channels of the streams. At that the gas-collecting mains are communicating with the adjacent channels separately. The reactor realizes feeding of the various gaseous mixtures in the adjacent channels , which may be under the different pressures, and the corresponding chemical reactions in them are also different. When one of the reactions is endothermic reaction, then the other reaction is exothermal; the heat is transmitted through the sheets separating the adjacent channels from the exothermic reaction to the endothermal reaction. The reactor may be used in the compact-type installation for realization of conversion of the methane with the steam, for production of the necessary heat at the methane catalytic combustion, and also Fisher-Tropsh synthesis, so this general method includes conversion of the methane in the long-chain hydrocarbons. The technical result of the invention is realization of the gaseous phases reactions at the increased pressures and especially for realization of the highly exothermal and endothermal reactions.

EFFECT: the invention ensures realization of the gaseous phases reactions at the heightened pressures and especially for realization of the highly exothermal and endothermal reactions.

9 cl, 6 dwg

FIELD: disproportionation process catalysts.

SUBSTANCE: invention relates to generation of hydrogen through steam conversion of carbon monoxide and development of catalyst for indicated process. Invention provides carbon monoxide conversion catalyst showing high catalytic activity and heat-conductivity and a process of steam conversion of carbon monoxide using indicated catalyst. Catalyst is characterized by heat-conductivity at least 1 W(mK)-1, which enables performing process with low temperature gradient in direction transversal to gas stream direction.

EFFECT: increased catalytic activity and heat-conductivity.

7 cl, 4 dwg, 3 tbl, 10 ex

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: process comprises contacting hydrocarbon blend with solid porous phase, namely with methanol decomposition catalyst or methanol-to-hydrocarbons and water conversion catalyst. Contact is conducted such that at least part of hydrocarbon blend comes into contact with catalyst under suitable conditions for conversion of at least part of methanol at volumetric feed flow rate 3-15 h-1.

EFFECT: enabled removal of methanol without disturbing composition of hydrocarbon blend.

4 cl, 7 ex

FIELD: hydrocarbon conversion catalysts.

SUBSTANCE: catalyst for generation of synthesis gas via catalytic conversion of hydrocarbons is a complex composite composed of ceramic matrix and, dispersed throughout the matrix, coarse particles of a material and their aggregates in amounts from 0.5 to 70% by weight. Catalyst comprises system of parallel and/or crossing channels. Dispersed material is selected from rare-earth and transition metal oxides, and mixtures thereof, metals and alloys thereof, period 4 metal carbides, and mixtures thereof, which differ from the matrix in what concerns both composition and structure. Preparation procedure comprises providing homogenous mass containing caking-able ceramic matrix material and material to be dispersed, appropriately shaping the mass, and heat treatment. Material to be dispersed are powders containing metallic aluminum. Homogenous mass is used for impregnation of fibrous and/or woven materials forming on caking system of parallel and/or perpendicularly crossing channels. Before heat treatment, shaped mass is preliminarily treated under hydrothermal conditions.

EFFECT: increased resistance of catalyst to thermal impacts with sufficiently high specific surface and activity retained.

4 cl, 1 tbl, 8 ex

FIELD: power engineering.

SUBSTANCE: method includes searching for continental or oceanic rift generation zones, supported by abnormal mantle with output of substance branches to earth crust. Drilling of wells by turbodrills into mantle substance. After well enters mantle substance a reaction hollow is formed in it by putting together force and product wells or by expanding force and/or product wells. Water is pumped into force well and gas-like hydrogen is outputted to surface through product well forming during reaction of inter-metallic substances fro mantle substance to water. Water is fed in amount, adjusting output of hydrogen, while reaction surface of reaction hollow is periodically regenerated, for example, by high pressure water flow, supplied through jets in reaction hollow, on remotely controlled manipulators. Expansion of well may be performed via explosions of explosive substances charges, and it is possible to separate forming gaseous hydrogen and water steam by separator mounted therein.

EFFECT: higher effectiveness of hydrogen production.

9 cl

FIELD: alternative fuel production and catalysts.

SUBSTANCE: invention relates to (i) generation of synthesis gas useful in large-scale chemical processes via catalytic conversion of hydrocarbons in presence of oxygen-containing components and to (ii) catalysts used in this process. Catalyst represents composite including mixed oxide, simple oxide, transition element and/or precious element, carrier composed of alumina-based ceramic matrix, and a material consisting of coarse particles or aggregates of particles dispersed throughout the matrix. Catalyst has system of parallel and/or crossing channels. Catalyst preparation method and synthesis gas generation method utilizing indicated catalyst are as well described.

EFFECT: enabled preparation of cellular-structure catalyst with high specific surface area, which is effective at small contact times in reaction of selective catalytic oxidation of hydrocarbons.

6 cl, 2 tbl, 16 ex

FIELD: autothermal catalytic reforming of hydrocarbon feed stream.

SUBSTANCE: method relates to method for reforming of hydrocarbon feed stream with water steam at elevated temperature to produce gas enriched with hydrogen and/or carbon oxide. Hydrocarbon stream is passed through water steam reforming catalyst bed wherein oxygen is fed through oxygen-permeable membrane followed by removing of finished product from this bed. Said catalyst bed contains in input region catalyst with reduced or without water steam reforming activity, but having hydrocarbon feed oxidation activity.

EFFECT: process with improved characteristics due to temperature controlling in reactor.

3 cl, 1 dwg

FIELD: alternate fuel manufacture catalysts.

SUBSTANCE: invention relates to generation of synthesis gas employed in large-scale chemical processes such as synthesis of ammonia, methanol, higher alcohols and aldehydes, in Fischer-Tropsch process, and the like, as reducing gas in ferrous and nonferrous metallurgy, metalworking, and on gas emission detoxification plants. Synthesis gas is obtained via catalytic conversion of mixture containing hydrocarbon or hydrocarbon mixture and oxygen-containing component. Catalyst is a complex composite containing mixed oxide, simple oxide, transition and/or precious element. Catalyst comprises metal-based carrier representing either layered ceramics-metal material containing nonporous or low-porosity oxide coating, ratio of thickness of metallic base to that of above-mentioned oxide coating ranging from 10:1 to 1:5, or ceramics-metal material containing nonporous or low-porosity oxide coating and high-porosity oxide layer, ratio of thickness of metallic base to that of nonporous or low-porosity oxide coating ranging from 10:1 to 1:5 and ratio of metallic base thickness to that of high-porosity oxide layer from 1:10 to 1:5. Catalyst is prepared by applying active components onto carrier followed by drying and calcination.

EFFECT: increased heat resistance and efficiency of catalyst at short contact thereof with reaction mixture.

13 cl, 2 tbl, 17 ex

FIELD: electric power and chemical industries; methods of production of the electric power and liquid synthetic fuel.

SUBSTANCE: the invention presents a combined method of production of the electric power and liquid synthetic fuel with use of the gas turbine and steam-gaseous installations and is dealt with the field of electric power and chemical industries. The method provides for the partial oxidation of hydrocarbon fuel in a stream of the compressed air taken from the high-pressure compressor of the gas turbine installation with its consequent additional compression, production of a synthesis gas, its cooling and ecological purification, feeding of the produced synthesis gas in a single-pass reactor of a synthesis of a liquid synthetic fuel with the partial transformation of the synthesis gas into a liquid fuel. The power gas left in the reactor of synthesis of liquid synthetic fuel is removed into the combustion chamber of the gas-turbine installation. At that the degree of conversion of the synthesis gas is chosen from the condition of maintenance of the working medium temperature at the inlet of the gas turbine depending on the type of the gas-turbine installation used for production of the electric power, and the consequent additional compression of the air taken from the high-pressure compressor of the gas-turbine installation is realized with the help of the gas-expansion machine powered by a power gas heated at the expense of the synthesis gas cooling before the reactor of synthesis. The invention allows simultaneously produce electric power and synthetic liquid fuels.

EFFECT: the invention ensures simultaneous production of electric power and synthetic liquid fuels.

2 cl, 2 dwg

FIELD: petrochemical industry.

SUBSTANCE: the invention is dealt with petrochemical industry, in particular with a method of catalytic preliminary reforming of the hydrocarbon raw materials containing higher hydrocarbons. The method provides for the indicated hydrocarbon raw materials gating through a zone of a catalyst representing a fixed layer containing a noble metal on magnesia oxide (MgO) and-or spinel oxide (MgAl2O4) at presence of oxygen and water steam. The technical result is a decrease of a carbon share on the catalyst.

EFFECT: the invention allows to decrease a carbon share on the catalyst.

3 cl, 2 tbl, 2 ex

FIELD: technology for production of methanol from syngas.

SUBSTANCE: claimed method includes mixing of hydrocarbon raw material with water steam to provide syngas by steam conversion of hydrocarbon raw material and subsequent methanol synthesis therefrom. Conversion of hydrocarbon raw material and methanol synthesis are carried out under the same pressure from 4.0 to 12.0 MPa. In one embodiment hydrocarbon raw material is mixed with water steam and carbon dioxide to provide syngas by steam/carbonic acid conversion of hydrocarbon raw material in radial-helical reactor followed by methanol synthesis therefrom under the same pressure (from 4.0 to 12.0 MPa). In each embodiment methanol synthesis is carried out in isothermal catalytic radial-helical reactor using fine-grained catalyst with grain size of 1-5 mm. Methanol synthesis is preferably carried out in two steps with or without syngas circulation followed by feeding gas from the first or second step into gasmain or power plant.

EFFECT: simplified method due to process optimization.

12 cl, 3 tbl, 3 dwg

FIELD: methods of production a synthesis gas.

SUBSTANCE: the invention is pertaining to the process of production of hydrogen and carbon oxide, which mixture is used to be called a synthesis gas, by a selective catalytic oxidation of the hydrocarbonaceous (organic) raw material in presence of the oxygen-containing gases. The method of production of the synthesis gas includes a contacting with a catalyst at a gas hourly volumetric speed equal to 10000-10000000 h-1, a mixture containing organic raw material and oxygen or an oxygen-containing gas in amounts ensuring the ratio of oxygen and carbon of no less than 0.3. At that the process is conducted at a linear speed of the gas mixture of no less than 2.2 · 10-11 · (T1 + 273)4 / (500-T2) nanometer / s, where: T1 - a maximum temperature of the catalyst, T2 - a temperature of the gas mixture fed to the contacting. The linear speed of the gas mixture is, preferably, in the interval of 0.2-7 m\s. The temperature of the gas mixture fed to the contacting is within the interval of 100-450°C. The maximum temperature of the catalyst is within the interval of 650-1500°C. The technical effect is a safe realization of the process.

EFFECT: the invention ensures a safe realization of the process.

10 cl, 5 ex

FIELD: chemical industry; petrochemical industry; oil refining industry and other industries; methods of production a synthesis gas.

SUBSTANCE: the invention is pertaining to the field of the methods of production of a synthesis of gas and may be used in chemical, petrochemical, oil refining and other industries. The method of production of synthesis gas using a vapor or a vapor-carbon dioxide conversion of a hydrocarbonaceous raw material provides for purification of the hydrocarbonaceous raw material from sulfuric compounds, its commixing with steam or with steam and carbon dioxide with formation of a steam-gas mixture. The catalytic conversion of the steam-gas mixture is conducted in a reactor of a radially-spiral type, in which in the ring-shaped space filled with a nickel catalyst with a size of granules of 0.2-7 mm there are the hollow spiral-shaped walls forming the spiral-shaped channels having a constant cross section for conveyance of a stream of the steam-gaseous blend in an axial or in a radially-spiral direction. At that into the cavities of the walls feed a heat-transfer agent to supply a heat into the zone of reaction. The invention ensures intensification the process.

EFFECT: invention ensures intensification the process.

4 cl, 4 dwg, 2 tbl, 3 ex

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