EA041315B1 - CATALYSTS, RELATED METHODS AND REACTION PRODUCTS - Google Patents

Description

Technical field

In general, the invention relates to improved catalysts providing reduced product contaminants, associated processes, and improved reaction products. More specifically, the present invention relates to improved direct fuel production and redox catalysts providing reduced levels of certain oxygenated contaminants, methods associated with the use of these catalysts, and fuel or fuel-related products having improved performance.

State of the art

The integrated conversion of gas-phase hydrocarbon resources into liquid hydrocarbons and fuels usually consists of six main processes (A. de Klerk: Fischer-Tropsch (F-T) Refining, Wiley Verlag, 2012). These processes include: 1) production and purification of synthesis gas; and 2) catalytically converting the synthesis gas into liquid hydrocarbons (fuels), catalyst reaction water, tail gas, and wax; 3) separation and collection of liquid hydrocarbons, catalyst reaction water and wax from the tail gas; 4) recirculation of the tail gas to obtain additional amounts of synthesis gas and/or for use as fuel oil; 5) upgrading/refining waxes to produce fuels and chemicals; and 6) purification and pretreatment of the catalyst reaction water prior to recycling, reuse and/or disposal.

The relative proportions of tail gas, liquid hydrocarbons, catalyst reaction water and wax depend on the type and composition of the catalyst; composition and purity of synthesis gas; type and design of the catalytic reactor; and operating conditions of the catalyst.

Synthesis gas can be obtained from many types of carbonaceous resources, including natural gas, coal, biomass, or virtually any hydrocarbon feedstock, through gasification or thermochemical conversion processes. Syngas production is generally classified into processes that: 1) use oxygen or air, or 2) processes that do not use oxygen or air.

Despite the work that has been done in this area, there is still a need in the art for new and improved catalysts, related processes, and improved reaction products.

Brief description of the invention

Embodiments of the present invention provide improved methods that enable direct recycling of catalyst reaction water to hydrocarbon synthesis gas production processes without the need for water purification and other water pretreatment methods described in the state of the art.

Suggested improvements include: 1) an improved direct fuel catalyst synthesized using a support whose surface has a neutral pH (eg, the surface is neither acidic nor basic); and 2) an improved redox catalyst that is used in conjunction with an improved direct fuel catalyst.

The combination of these innovations results in catalyst reaction water free of harmful carboxylic acids, and as a result, such catalyst reaction water can be recycled directly to the synthesis gas production process.

This improved redox catalyst has been designed to be regenerated (activated) and operate efficiently under the same temperature, pressure and space velocity conditions as the improved direct fuel catalyst.

As a result, the only oxygenated hydrocarbons present in the catalyst reaction water are non-corrosive hydroxyalkanes (eg, alcohols) that are efficiently reformed using catalytic and non-catalytic steam reforming processes.

Such improvements can significantly reduce and in many cases eliminate the need for an external supply of treated water. In addition, the complex and costly problem of wastewater disposal is reduced or eliminated.

Direct catalytic reforming of the recycled catalyst water of reaction containing hydroxyalkanes helps to reduce the ratio of hydrogen to carbon monoxide to an ideal H ₂ /CO stoichiometric ratio of about 1.8-2.4/1.0.

In one aspect, the present invention relates to a process for converting one or more carbonaceous feedstocks to one or more hydrocarbons (eg, liquid fuels). The proposed method includes the steps of: converting one or more carbonaceous raw materials into synthesis gas; and converting the synthesis gas to one or more hydrocarbons (eg liquid fuels) and an aqueous fraction. The aqueous fraction contains less than 500 ppm of one or more carboxylic acids.

According to another aspect, the present invention relates to a direct conversion system

- 1 041315 synthesis gas into hydrocarbons (for example, liquid fuels). The proposed system includes: a synthesis gas generator containing a device for converting one or more carbonaceous raw materials into synthesis gas; a catalytic reactor containing a conversion catalyst for converting synthesis gas into one or more hydrocarbons (for example, liquid fuels) and an aqueous fraction, while said conversion catalyst contains a carrier, while said carrier has a surface whose pH is from about 6.0 to about 8.0.

Brief description of graphic materials

In FIG. 1 shows a flow diagram of a preferred embodiment of a distributed conversion process including a contaminant removal process 102 by introducing a carbonaceous feedstock 101 as a gas; a synthesis gas generator 103 for producing synthesis gas from carbonaceous raw materials; removing harmful contaminants that may be present in the synthesis gas 105; the process of adjusting the ratio of H ₂ /CO in the synthesis gas 106, if necessary; compressing the synthesis gas, if required; catalytic reactors (preferably tubular design) 108; improved redox catalyst to remove any oxygen in syngas 109a integrated in tubular catalytic reactors with improved direct fuel catalyst 109b.

The tail gas, liquid fuel, catalyst reaction water and wax are separated 110 into four fractions. Since the catalyst water does not contain harmful carboxylic acids, it can be directly recycled 112 to the synthesis gas generator 103 or used for other purposes such as injection 119 for secondary and tertiary oil recovery;

in fig. 2 - improved redox catalyst;

in fig. 3 - distillation of liquid fuels to obtain high-quality fuel products.

Detailed description of the invention

The present invention relates to an improved process for direct recycling of catalyst end water to a gas-to-liquid, biomass-to-liquid, coal-to-liquid, or other XTL process (where XTL refers to the conversion of any carbonaceous material to liquid fuels). The formation of harmful carboxylic acids in the catalyst reaction water (and fuels) is eliminated by using an improved catalyst for the direct production of liquid fuels synthesized from carriers having a neutral pH surface and other key properties. In addition, if oxygen levels in the synthesis gas are high, an improved redox catalyst is used that reduces the oxygen concentration in the synthesis gas by more than 95%. These innovations can be used independently or they can be used in combination, in which a redox catalyst is used together with an improved catalyst for the production of liquid fuels, while both catalysts are activated (reduced) and operate under similar conditions. Because no hazardous carboxylic acids are generated, the catalyst reaction water can be recycled and used directly in syngas processes without the need for water treatment processes that have traditionally been used to remove harmful carboxylic acids and other unwanted water contaminants prior to use.

Methods for producing synthesis gas that use oxygen.

Syngas processes that use O2 or air are commonly referred to as direct conversion or partial oxidation (POX) processes. POX is carried out with substoichiometric hydrocarbon/oxygen gas mixtures in reformers at temperatures ranging from 1500 to 2700°F (about 815 to 1480°C). Praxair, Shell, ConocoPhillips and others have developed systems for converting gaseous hydrocarbon resources into syngas using ROX. Each of these systems uses an oxygen supply, which requires compressed oxygen to be delivered to the plant using one of the methods described above. For example, the Praxair method uses a hot oxygen burner that is non-catalytic and converts natural gas (or other hydrocarbons) and oxygen into syngas, as described in US Pat. No. 8,727,767 (5/2014).

ConocoPhillips uses a catalyst in its thermochemical conversion system described in US Pat. No. 7,261,751 (8/2007). In industrial practice, steam is introduced into the ROX reformer to minimize the formation of elemental carbon and to help increase the H2/CO ratio, as described in US Pat. No. 6,942,839 (9/2005) to Shell.

There are some disadvantages associated with the use of ROX for micro and small GTL (Gas to Liquid) installations:

1) any ROX process that uses oxygen requires co-location of an oxygen production plant, and depending on the oxygen production method, such oxygen may contain concentrations of other gases such as nitrogen and argon;

2) additional routine operations are usually required to bring H2/CO to ideal stoichiometric ratios of approximately 1.8 to 2.3;

- 2 041315

3) nitrogen present in the feed or present in the oxygen stream can form NH3 and HCN contaminants in the syngas stream, which are potential catalyst poisons;

4) in addition, nitrogen dilutes the synthesis gas, which requires an increase in the scale of thermochemical and catalytic processes;

5) the presence of unreacted oxygen in the thermochemical process can lead to the formation of carboxylic acids in the synthesis gas. Some of these carboxylic acids in the synthesis gas may move through the catalysts and eventually end up in the catalyst reaction water, liquid fuels and waxes;

6) the presence of oxygen in the synthesis gas can lead to the formation of carboxylic acids during the catalytic conversion of synthesis gas to hydrocarbon products, depending on the chemical and physical properties of the catalyst used and the concentration of oxygen in the synthesis gas; And

7) the presence of unreacted oxygen in the synthesis gas can lead to oxidation of the reduced catalyst, making it less efficient in terms of producing fuels.

Autothermal reforming (ATR) is another group of conversion technologies that use catalysts to produce synthesis gas from gaseous hydrocarbons, oxygen and steam. Shell has described the ATR process in their US patents WO 2016016256 (2/2016) and WO 2006037782 (4/2006). There are several disadvantages to using ATR: 1) the catalyst is expensive and may have a limited lifespan; 2) catalytic reformers are large and expensive; 3) a combined oxygen production plant is required, which adds significant capital costs and can, in some cases, double the plant's energy requirements; and 4) in some cases, the H ₂ /CO ratio may be too low or too high, and additional routine processes are required to separate hydrogen to reduce H 2 /CO to the desired stoichiometric ratio.

There is some limited data available on the oxygen concentration in synthesis gas from gasification processes that use oxygen or air. Babcock and Wilcox found that residual oxygen in synthesis gas from gasification of solid phase carbonaceous raw materials with air was in the range of 4000 to 6000 ppm (Treepower, 2016). However, in some cases, the residual oxygen in the synthesis gas can be as high as 10,000 ppm (Yun, 2003).

It has been found that when oxygen is present during the thermochemical conversion of carbonaceous materials, the formation of contaminants such as carboxylic acids is greatly increased, and that some of such oxygen may remain in the synthesis gas depending on the type of thermochemical conversion process and operating conditions ( Schuetzle et al., 2015). Carboxylic acids are of particular concern because they can corrode metal surfaces and deactivate catalysts. Such carboxylic acids may also elute through the catalytic reactor and partition into the fuel and catalyst reaction aqueous products.

Methods for producing synthesis gas that do not use oxygen.

The conversion of solid and liquid phase carbonaceous feedstocks to synthesis gas using steam in the absence of oxygen or air is commonly referred to as indirect thermochemical conversion.

Steam methane reforming (SMR) is a well-established process for converting gas-phase hydrocarbons into synthesis gas. Because methane is difficult to efficiently steam reform to produce synthesis gas at temperatures below about 2200°F (about 1200°C), catalysts are commonly used to lower the reforming temperature to about 1600-1700°F (about 870-930°C). This process is called catalytic methane steam reforming (CSMR) and is very efficient in reforming other gas phase hydrocarbons such as _C2 - _C16 hydrocarbons and Ci-Cig hydroxyalkanes and C3-C16 ketones (Sa et al., 2010).

These non-oxidative processes produce synthesis gas typically containing less than about 500-1000 ppm oxygen.

Effect of pollutants on catalysts.

In table. Table 1 lists some of the potential catalyst contaminants found in syngas and the maximum recommended levels of such contaminants. Numerous methods exist in the art for removing hydrogen sulfide, sulfur dioxide, ammonia, hydrogen cyanide, nitrogen oxides, hydrogen chloride, and particulate matter contained in synthesis gas. However, little attention has been paid to oxygen removal, which is important because it has been found that oxygen levels above about 500 ppm in synthesis gas generation processes lead to a significant increase in the formation of synthesis gas contaminants (Schuetzle et al., 2015), with residual oxygen in synthesis gas will re-oxidize the reduced catalyst, which reduces the efficiency of fuel production.

Harmful carboxylic acids can be formed when oxygen reacts with free radicals during the catalytic conversion of syngas with CO and H2. The formation of these acids depends on the oxygen concentration in the synthesis gas, the chemical and physical properties of the catalyst, and the operating conditions of the catalytic reactor. When carboxylic acids are formed, they will be approximately distributed between the liquid fuel, catalyst reaction water and wax, as indicated in table. 2.

Table 1. Potential Syngas Catalyst Contaminants and Their Maximum Recommended Levels for Existing Catalysts Used to ___________ Convert Syngas to , Hydrocarbon Products___________

Catalyst contaminants Maximum recommended contaminant levels Hydrogen sulfide (H2S) < 20 ppb Sulfur dioxide (SO2) < 200 ppb Ammonia (NH3) < 5ppm Hydrogen cyanide (HCN) < 20 ppb Nitrogen oxides (NOx) < 200 ppb Hydrogen chloride (HC1) < 35 ppb Oxygen (O2) < 500 ppb Total particulate matter (PM2.5) < 500 µg/m ³

When such carboxylic acids are present in fuels, the fuel can corrode metal surfaces and the shelf life of the fuel is greatly reduced. Therefore, these acids must be removed (if present) from the fuel prior to distribution, storage and use, and this process is complex and costly.

At the same time, when these carboxylic acids are present in the catalyst reaction water, they must be removed before the water can be recycled and used for production processes. Along with the problem of metal surface corrosion, such acids will damage the catalysts commonly used in catalytic steam reforming processes.

Table 2. Relative distribution of carboxylic acids (if formed) _______ in catalyst reaction water, liquid fuels and wax _______

carboxylic acid Boiling point (°C) Distribution (mole percent) Water liquid fuels Wax Methane (ant) 101 100 0 0 Ethane (acetic) 118 100 0 0 propane 141 75 25 0 Butane 164 thirty 70 0 Pentane 187 10 85 5 Hexane 205 5 80 15 Octane 239 <1 75 25

Purification of synthesis gas.

In the modern art, there are many methods for purifying synthesis gas before catalytically converting synthesis gas into hydrocarbon products. The concentration of contaminants depends on the type of thermochemical conversion process used and the feedstock composition (Schuetzle et al., 2015). Thermochemical conversion of gas-phase hydrocarbons provides much lower concentrations of pollutants in the synthesis gas than the conversion of solid carbonaceous materials such as biomass, coal, municipal solid waste and other solids. Sulfur compounds are the most common pollutants in gas phase hydrocarbon resources. Such contaminants can be removed using a variety of solid phase binders such as iron oxide or zinc oxide.

Removal of oxygen from synthesis gas.

There are very few ways to remove oxygen from syngas. This section summarizes the state of the art used to remove oxygen from synthesis gas.

A typical industrial process for removing oxygen from industrial gas streams such as N ₂ , Ar, He, Ne, etc., has been carried out by reacting with an excess of hydrocarbons (CH4, H2, etc.) in heated catalyst beds. With this method, water is formed, which is removed by drying the gas stream with adsorbents.

US Pat. No. 6,744,066 (6/2004) describes a process for oxygen reduction in synthesis gas and the use of oxygen reduced synthesis gas to produce hydrocarbon products. The authors describe a catalyst, aPt-eCeO ₂ -YAl ₂ O ₃ , which promotes the reaction between oxygen and carbon monoxide in a synthesis gas stream containing a lower oxygen concentration, as shown in equation 1

O2 + 2CO = 2COg Equation 1

Such a catalyst is effective in reducing the oxygen concentration in the synthesis gas in the presence of oxygen in concentrations up to 1000 ppm. However, the efficiency of such a catalyst in terms of oxygen reduction is not reported. Since this catalyst reduces the concentration of CO, the production of hydrocarbon products will also decrease.

US Pat. No. 5,607,572 (3/1997) describes the use of a metal oxide supported on a high specific surface area to remove oxygen from gas streams. The metal oxide is first reduced to its elemental (metallic) state with a reducing gas (eg H ₂ ) in a separate process at high temperatures up to 1500°C. In the gas stream, the metal reacts with oxygen, which forms the metal oxide. After a selected period of time, the metal oxide is re-reduced with H ₂ at temperatures up to 1500°C.

Catalytic conversion of synthesis gas into products.

There is a significant amount of prior art that describes the conversion of synthesis gas into products. Several recent reviews have fairly well summarized and compared the strengths and weaknesses of these different ways of converting syngas to fuels.

There are two main approaches for the catalytic conversion of synthesis gas to fuels: 1) catalytic conversion of synthesis gas to intermediate products (mainly wax), followed by costly wax upgrading and refining processes such as hydrocracking and; 2) direct catalytic conversion of synthesis gas into fuel, which produces a minimum amount of wax [US patents 8394862 (8/2013) and 9090831 (7/2015)].

All modern medium to large industrial scale GTL plants are capable of converting synthesis gas to wax as the main product. Refining/enrichment processes are then used to obtain fuels and other products from the wax. Since such refining processes are complex and expensive, fuel production costs can increase by more than 40% relative to direct production methods.

Medium to large plant designs that incorporate traditional Fischer Tropsch processes and use wax hydrocracking and other costly upgrades are not economically viable for distributed plants that process smaller volumes of gas phase hydrocarbons.

Micro GTL plants include processes to convert approximately 0.25 to 1.0 million standard cubic meters. feet/day (from about 7080 to 28300 cubic meters/day) of gas-phase hydrocarbons in about 25 to 100 barrels/day (from about 4 to 16 cubic meters/day) of liquid fuels. GTL plants, which convert approximately 1.0 to 25 million standard cubic meters. ft/day (about 28,300 to 707,900 cubic meters/day) of gas phase hydrocarbons in about 100 to 2,500 barrels/day (about 16 to 400 cubic meters/day) of fuel, commonly referred to as small GTL units.

catalytic reactors.

There are several types of catalytic reactors that have been commercialized on an industrial scale for the catalytic conversion of synthesis gas to hydrocarbon products.

Multitubular fixed bed catalytic reactors consist of a plurality of small diameter tubes that are used and contain a catalyst. These tubes are placed inside the reactor vessel, in which water circulates to remove the exothermic heat released during the conversion of synthesis gas into hydrocarbon products. The use of catalysts that form heavy waxes can lead to coating of the catalyst, resulting in a significant reduction in the efficiency of the catalyst. Such reactors operate in a multi-pass mode with the removal of products after each run and the recirculation of unreacted synthesis gas back to the catalytic reactors. Typically, two to three passes through these reactors will convert about 90% by volume of CO into hydrocarbon products. Multitubular reactors can be effectively scaled down for use in small and micro scale GTL plants.

Slurry reactors use finely divided catalysts suspended in a liquid medium. Heat removal is carried out using internal cooling coils. Synthetic gas is bubbled through the liquid medium, which also ensures mixing of the reactor contents. The small particle size of the catalyst improves the mass transfer of heat to the liquid medium. The separation of waxy products from the catalyst particles has been a problem, but in the case of large-scale installations, improved separation methods have been developed and successfully implemented. However, such separation methods are complex and costly and therefore slurry reactors cannot be efficiently and economically scaled down for use in small and micro scale GTL plants.

Microchannel reactors consist of reactor cores containing thousands of thin process channels filled with very small particle size catalysts. Such reactor cores alternate with channels ranging in size from 0.1 to 10 mm containing an aqueous coolant. Because the catalyst particles and channels are small, heat can be dissipated more quickly than with conventional tubular reactors of 25 to 40 mm.

Although microchannel reactors may have higher CO conversions per run, there are several potential difficulties: 1) these reactors do not handle solids very well, leading to channel plugging; 2) mechanical pumping can generate pulsating flow which causes problems; 3) when moving from a demonstration to an industrial scale, it is not possible to easily change the large area-to-volume ratio and the uniform residence time; 4) corrosion can be a major problem due to thin walls; 5) since wax is the main hydrocarbon product, heavy fractions of wax (C ₅₀ -C ₁₀₀ ) can easily clog microchannels; 6) only finely divided catalysts can be used, and not innovative catalysts that have certain shapes (for example, shamrocks), aspect ratios and sizes; (7) Ensuring accurate temperature control in shallow channels is a challenge. Some examples of the field of technology associated with microchannel reactors are given in US patent No. 8043571; 7744829; 7470405; 7,404,936 (7/2008) and U.S. Patent Application Publications 2015/0259609 and 2014/0140896.

Converting synthesis gas to waxes.

Many catalysts and catalytic processes have been developed and implemented to convert synthesis gas to wax. Such catalysts are commonly referred to as Fischer-Tropsch (F-T) catalysts (Jahangiri et al., 2014).

US Pat. No. 6,262,131 (7/2001) describes a Fischer-Tropsch structured catalytic system and a Fischer-Tropsch process comprising at least one structure having a catalytic surface, such catalytic surface having a linear dimension greater than 20 mm, a void ratio greater than 0, 6 and a circuit that causes non-Taylor flow as CO and H ₂ pass through said structure. This patent describes Fischer Tropsch catalysts, including iron and cobalt.

US Pat. No. 5,620,670 (4/1997) describes a catalytic process for converting synthesis gas in a Fischer-Tropsch synthesis reactor by using a promoted iron oxide catalyst slurry.

US Pat. No. 4,499,209 (2/1985) describes a Fischer-Tropsch catalyst prepared by impregnating a silica support with a solution of zirconium and titanium, followed by calcination and other preparation steps.

The listed patents describe catalysts that produce high molecular weight hydrocarbon reaction products (eg, wax) that require further processing, including hydrotreating and other quality enhancement methods, to produce diesel fuel or a diesel fuel blending component.

Direct conversion of syngas to liquid fuels.

The direct efficient conversion of syngas to liquid fuels instead of wax eliminates the need for complex and costly purification processes required to convert wax to fuels. Examples of the state of the art related to the direct production of liquid fuels from synthesis gas are given below.

US Pat. Nos. 8,394,862 (8/2013) and 9,090,831 (7/2015) describe a unique process and catalyst that works effectively in the direct production of a high cetane diesel type fuel or diesel blending component from stoichiometric mixtures of hydrogen and carbon monoxide. The present invention provides, but is not limited to, economical and efficient production of high quality diesel fuels in small or distributed fuel production plants with an annual production capacity of less than 100 million gallons (about 380 million liters) per year, by eliminating conventional hydrocracking and other expensive enrichment methods. Such a catalytic process is ideal for distributed diesel production plants such as biomass fuel production plants, tight natural gas diesel production plants, flared gas to fuel conversion and other applications requiring an optimized economy based on on the use of distributed resources of raw materials.

When using a direct fuel catalyst, no carboxylic acids are formed when the surface of the catalyst support is neutral or very close to neutral (pH in the range of 6.0 to 8.0, ideally about 7.0). This is due to the fact that the acidic surface consists of OH groups. For example, if the carrier is alumina, the surface composition is Al-OH. With a neutral alumina surface, the surface composition is Ai-O-Ai.

The acidity of the surface of the catalyst support can be easily measured. One preferred method uses a measurement obtained by colorimetric titration with propylamine using methyl red indicator, the neutral surface being defined as

- 6 041315 surface for which the acidity of the surface is less than about 0.5 mmol per gram.

OH groups in an acidic support (Al-OH) can react with alkoxy radicals (CHO*) to form acids, as shown in equation 2. It is well known that methyl radicals (CH3*) are common intermediates formed during the catalytic conversion of synthesis gas. When O ₂ is present in the syngas, oxygen reacts rapidly with CH3* to form methoxy radicals (HCO*) as shown in equation 2. These methoxy radicals can then extract the OH moiety from the AlOH surface to form formic acid, as shown in equation 3. Other acids can be formed in a similar way (for example, malonic, butyric, pentanoic, etc.).

CH3 * + O ₂ \u003d HCO * + H ₂ O Equation 2

HCO* + AlOH = HCOOH + A1* Equation 3

Al* then rapidly reacts with water to re-form AlOH and H* hydrogen radicals.

Alkoxy radicals can form even with very little O2 present in the synthesis gas. When the surface of the catalyst support is neutral, no organic acids are formed even if some alkoxy radicals are formed.

To eliminate the formation of organic acids during the catalytic conversion of synthesis gas to hydrocarbon products, two innovations can be used individually or in combination. The first innovation involves the production of catalysts using carriers whose surface has a neutral pH (about 7.0). The second innovation is the development of a new redox catalyst designed to reduce the oxygen content of syngas to very low levels (less than 500-1000 ppb).

Collection and separation of products.

In general, using a three-phase separator, the product stream from the catalytic reactor is separated into the following fractions: tail gas; condensed liquid hydrocarbons, catalyst reaction water and waxes. The tail gas fraction typically consists of H2, CO, CO2 and C1- _C5 hydrocarbons and oxygenated organic compounds; the condensed fraction contains approximately C ₅ -C ₂₄ hydrocarbons and oxygenated organic compounds; the wax fraction contains approximately C ₂₃ -C ₁₀₀ hydrocarbons and the reaction water fraction consists of water containing from about 1.0 to 5.0% by volume of dissolved oxygenated organic compounds.

Since the synthesis gas catalytic conversion efficiency is typically between 90% and 93% when using tail gas recycle tubular reactors, some H2 and CO will remain in the tail gas. In addition, the tail gas contains some CH ₄ which is formed as a result of the catalytic reaction. The composition of the tail gas depends on the type of thermochemical process and operating conditions. Such tail gas may be recycled back to the thermochemical conversion system to produce additional synthesis gas and/or may be used as heating oil.

Although virtually all catalytic processes described in the state of the art have been used to convert synthesis gas primarily to wax, the improved catalyst described herein was designed primarily to produce C5-C24 hydrocarbon liquids and very little wax. (C ₂₄₊ hydrocarbons [0 to 25 vol%]). Therefore, the improvement of such a catalyst to produce a large amount of liquid fuel and a small amount of wax is an important key element of the present invention.

Purification of the catalyst reaction water using the prior art.

Numerous examples exist in the art that provide quantitative data on the concentrations of dissolved oxygenated organic compounds in catalyst reaction water. Such dissolved oxygenated organic compounds mainly consist of hydroxyalkenes (alcohols) and carboxylic acids with a total concentration ranging from 0.5 to 5.0% by volume depending on the thermochemical conversion method, the composition and purity of the synthesis gas and the type of catalyst and used catalytic process.

US Pat. No. 8,999,164 describes the preparation of catalyst water of reaction by Fischer-Tropsch synthesis gas catalysis, whereby the concentration of carboxylic acids in the water was found to be up to about 9000 ppm.

US Patent Application Publication 2014/102981 reports the presence of about 5000 ppm carboxylic acids in catalyst reaction water.

In US Pat. No. 8,535,487, it was found that when syngas was produced by a partial oxidation steam reforming process, carboxylic acids were present in the catalyst process water at concentrations of 5,000 to 15,000 ppm.

US Pat. No. 7,989,510 describes catalyst water of reaction produced in a partial oxidation catalytic steam reforming process and found that acids are present in concentrations of 5,000 to 15,000 ppm.

US Pat. No. 7,153,432 describes the preparation of catalyst water of reaction in which the acids were found to be between 750 and 12,000 ppm.

US Patent Application Publication 2003/106351 describes the production of process water from Fischer-Tropsch synthesis gas catalysis and found that carboxylic acids in the water fraction ranged from 900 to 14100 ppm.

When such carboxylic acids are formed during thermochemical and/or catalytic processes, they will be distributed in the catalyst reaction water; liquid fuels and wax, as shown earlier in table. 2.

If these carboxylic acids are present in the catalyst reaction water, such water cannot be recycled directly to the catalytic steam reforming process due to corrosion of the metal surfaces and deactivation of the reforming catalysts. For this reason, numerous procedures have been developed and used to purify such water prior to use in thermochemical processes, as well as for other purposes.

These methods included distillation, stripping, extraction, anaerobic digestion, biological oxidation, thermal oxidation, combinations thereof, and other water treatment methods.

US Pat. No. 9,067,806 (6/2015) describes a process for purifying an aqueous stream resulting from Fischer-Tropsch catalysis of synthesis gas, including the following treatment methods: neutralization of carboxylic acids with inorganic bases; evaporation, distillation and distillation of light fractions; and treatment with at least one organic base. Such a purification method makes it possible to use at least a part of the aqueous stream coming from the catalyst reaction water as process water in an industrial plant.

US Pat. No. 8,999,164 (4/2015) describes catalyst water of reaction obtained from Fischer-Tropsch synthesis gas conversion, consisting of the following oxygenated organic compounds: C1-C9 hydroxyalkanes (70% by weight); C ₂ -C ₆ organic acids (20 wt.%); salts of organic acids (2 wt.%); and ketones and aldehydes (8%). The concentration of hydroxyalkanes and organic acids in water was found to be 48,000 and 9,000 ppm, respectively. A method for removing hydroxyalkanes and organic acids by distillation is described. Fractions containing carboxylic acids are treated using anaerobic biological processes.

U.S. Patent Application Publication 2014/102981 (4/2014) describes a process for purifying an aqueous stream resulting from a Fischer-Tropsch reaction, comprising supplying an aqueous stream to one or more evaporation units through a semi-permeable baffle, resulting in an aqueous stream, enriched in oxygenated organic compounds, and an aqueous stream enriched in water. Such an aqueous stream is fed to a plant for producing synthetic gas.

US Pat. No. 8,591,737 (11/2013) describes a process for treating catalyst reaction water obtained from a biomass-to-liquid process, said process comprising producing syngas from biomass and converting syngas to liquid hydrocarbons via a Fischer-Tropsch process. Catalyst reaction water is treated in the same way as wastewater from another industrial process that integrates a biomass-to-liquid process, such as forestry, power and/or heat generation, waste incineration, or a process used in the petrochemical industry. and/or the oil refining industry. The biomass liquefaction process and the combined industrial process may have a common feed water process plant, a common cooling water process plant, and a common waste water treatment plant. The wastewater treatment process may include a biological treatment process, whereby a cobalt catalyst may be used in the Fischer-Tropsch process. A combined plant is also described, including a biomass-to-liquid plant and other industrial equipment, both of which are connected to a common wastewater treatment equipment.

U.S. Patent 8,535,487 (9/2013) relates to a process for purifying an aqueous stream resulting from a Fischer-Tropsch reaction, comprising feeding said aqueous stream into a system containing a distillation column equipped with a partial condenser and a full condenser, at least partially condensing the evaporated stream leaving from the head of the distillation column, and collecting the first distillate, consisting of heavier by-products, completely condensing the remainder of the vaporized stream leaving the partial condenser, and collecting the liquid stream, which is returned to the distillation column as reflux, and removing the purified water stream from the bottom parts of the distillation column.

US Pat. No. 8,529,865 (9/2013) describes a process for treating catalyst reaction water by distillation and/or light ends stripping to form an oxygenate-rich stream containing reformant and oxygenates coming from the final water. The oxygenate-rich stream is fed to a second synthesis gas generator and reformed under reforming conditions to form at least hydrogen.

U.S. Patent 8,158,029 (4/2012) describes a method for producing syngas from coal, including obtaining an oxygen stream in an air separation unit and humidifying the oxygen stream

- 8 041315 by bringing it into contact with a hot aqueous liquid to obtain a humidified oxygen stream. Humidified, heated oxygen-containing stream is fed into a low-temperature slag-free gasifier, in which carbon-containing material is gasified, thereby forming syngas, which is used for hydrocarbon synthesis according to Fischer-Tropsch. Purified water is mainly used to humidify the oxygen stream with a small make-up of catalyst water obtained from the Fischer-Tropsch process. The remaining catalyst reaction water is used as cooling water and for other production processes.

US Pat. No. 8,057,578 (11/2011) describes a water treatment process comprising bringing a first aqueous effluent containing one or more thermally degradable contaminants and one or more thermally indestructible contaminants into contact with steam to provide a second effluent containing steam and at least a portion of one or more thermally indestructible contaminants. The second effluent is treated in an acid recovery unit, wherein the intermediate effluent is treated with one or more oxidizers to form a third effluent. One or more oxidizing agents and at least a portion of one or more thermally degradable contaminants are destroyed using one or more incineration methods.

US Pat. No. 8,048,178 (11/2011) describes a wastewater treatment process for treating wastewater from a biomass-to-liquid (BTL) process that uses a Fischer-Tropsch process using a cobalt catalyst to convert syngas to liquid hydrocarbons. The aqueous effluent from the BTL process is treated in a general wastewater treatment process including a biological treatment process, along with wastewater from a combined pulp and/or paper process.

US Pat. No. 7,989,510 (8/2011) describes a process for purifying catalyst reaction water by using a fractionating distillation column and a stripping column. The separated oxygenated organics are sent to a thermochemical synthesis gas generator to produce additional synthesis gas.

US Pat. No. 7,323,497 (1/2008) describes a process using catalytic steam reforming followed by partial combustion with an oxygen-containing gas to form a reformed gas mixture. Water is separated from said reformed gas mixture and a dry gas is obtained. For the synthesis of hydrocarbons from said dry gas, a Fischer-Tropsch type catalyst is used. Catalyst reaction water containing alcohols, aldehydes, ketones and carboxylic acids is pre-treated to reduce fouling or corrosion in the saturator and water heat exchangers, for example by passing the water through filters and/or adjusting the pH. Part of the purified water is used as steam to obtain a reformed gas mixture.

US Pat. No. 7,318,894 (1/2008) describes a method and system for treating catalytic reaction water using membrane processes, preferably in combination with anaerobic biological treatment, which allows the water treatment process to be carried out without the bulk production of biological solids.

US Pat. No. 7,276,105 (10/2007) describes a process for separating water from a Fischer-Tropsch product stream, comprising feeding the Fischer-Tropsch product stream into a separation membrane, preferably a ceramic membrane, and extracting water vapor from the permeate side of the outlet side of the membrane. Purified water is used to generate steam for the steam methane reformer. The oxygenated hydrocarbons in the concentrated solute are destroyed using a thermal oxidizer.

US Pat. No. 7,235,172 (6/2007) describes a process for the production of olefins. Process water from the synthesis gas reactor, hydrotreating unit, water stripper, cooling unit, catalyst recovery unit, catalyst activation unit, and fractionator containing oxygenates and a naphtha stream is fed to a steam cracker to produce a product stream containing olefins. Water-soluble oxygenates (oxygen-containing organic compounds) include organic acids, alcohols, aldehydes, ketones, and esters.

US Pat. No. 7,166,219 (1/2007) describes a process for producing purified water from Fischer-Tropsch catalyst water of reaction, comprising: a first separation treatment to remove at least a portion of the non-acidic oxygenated hydrocarbons present to obtain a water-rich water stream; a second step comprising a biological treatment to remove at least a portion of the acids from at least a portion of the first water-rich water stream to obtain a second water-rich water stream; followed by a third stage, including separation into solid and liquid phases to remove at least some of the solid compounds from at least part of the second aqueous stream enriched in water.

US Pat. No. 7,153,432 (12/2006) describes a process for purifying catalyst reaction water co-formed in a Fischer-Tropsch reaction, comprising: (a) distillation or liquid-liquid

- 9 041315 new extraction of water, co-formed in the Fischer-Tropsch reaction, to remove at least part of the alcohols present in the specified water, and obtain a first stream enriched in water; and (b) subjecting said first water-rich stream to a separation process using membranes to remove at least a portion of the solids contained in the slurry, along with some organic acids, to obtain purified water. This membrane separation method can be selected from the group consisting of: microfiltration, ultrafiltration, reverse osmosis and evaporation through a semi-permeable septum.

US Pat. No. 7,150,831 (12/2006) describes a process for producing purified water from Fischer-Tropsch catalyst reaction water, comprising the following steps:

1) a first step comprising a separation treatment to remove at least a portion of the non-acidic oxygenated hydrocarbons present in the catalyst reaction water to obtain a first aqueous stream enriched in water;

2) a second stage comprising liquid-liquid extraction to remove at least a portion of organic acids from at least a portion of said first water-rich water stream to obtain a second water-rich water stream;

3) a third step comprising a biological treatment to remove at least a portion of the organic acids from at least a portion of said second water-rich water stream to form a third water-rich water stream;

4) the fourth stage, including the separation into solid and liquid phases to remove at least part of the solid compounds from at least part of the specified third aqueous stream enriched with water.

US Patent Application Publication 2005/113426 describes a process using Fischer-Tropsch catalyzed reaction water, including passing purified water from the distillation process to a saturation column. The steam obtained from the saturation column is used to saturate the hydrocarbon gas stream for the syngas plant.

US Pat. No. 7,147,775 (12/2006) describes a process for producing purified water from catalyst reaction water, consisting of the following steps:

1) biological treatment to remove at least a portion of the dissolved oxygenated organic compounds to obtain the original water stream;

2) separation into solid and liquid phases to remove part of the solid compounds from the original water stream;

3) removing dissolved salts of organic compounds from the second aqueous stream by chemical oxidation, ultraviolet light and adsorption/absorption processes (eg, with activated carbon);

4) biological treatment to remove at least a portion of the dissolved oxygenated organic compounds to obtain the original water stream;

5) separation into solid and liquid phases to remove part of the solid compounds from the original water stream;

6) removing dissolved organic salts from the second aqueous stream by chemical oxidation, ultraviolet light and adsorption/absorption processes (eg activated carbon).

US Pat. No. 6,887,908 (5/2005) describes the use of thermal oxidation to remove organics from catalyst reaction water. The present invention uses excess heat from a thermochemical process to vaporize water into steam and thermally oxidize organic pollutants. However, those skilled in the art of thermochemical processes are well aware that temperatures in excess of 1600°F (about 871°C) are required to convert these organic contaminants to synthesis gas. Since the concentration of such organic compounds is less than 5.0 mole percent, the ratio of water to organic carbon will be more than 25/1 compared to the ideal ratio of 1.5-2.5/1.0 for a thermal oxidation process. Accordingly, such a process would be energy intensive, inefficient and very expensive.

US Patent Application 2004/0262199 (12/2005) describes a method of feeding at least a portion of the gaseous crude product or final water into a distillation column on a feed tray; removing the liquid stream from the distillation column from a tray above the feed tray; separation of the liquid stream into an aqueous phase and a phase rich in non-acidic chemical compounds; and returning the aqueous phase to the distillation column to a tray below the tray from which the liquid stream was removed.

US Pat. No. 6,533,945 (3/2003) describes a process for treating water from a hydrocarbon synthesis reactor, which includes mixing catalyst reaction water with solid combustible organic fuel to form a slurry and gasifying such a slurry in oxygen blast gasifiers to produce synthesis gas at temperatures up to 2800° F (about 1540°C). The catalyst reaction water contains hydroxyalkanes (alcohols) and carboxylic acids.

- 10 041315

US Patent Application Publication 2003/1065351 describes catalyst water of reaction obtained by Fischer-Tropsch catalysis of synthesis gas, it was found that hydroxyalkanes and carboxylic acids in the aqueous fraction ranged from 1.0 to 4.5 wt.%. and from 0.09 to 1.41 wt.%, respectively. The water is purified by a primary biological treatment followed by a secondary solid-liquid separation and a final tertiary treatment.

US Pat. No. 5,053,581 (10/1991) relates to a process for recycling condensate from the synthesis of hydrocarbons or alcohols, said condensate containing water and contaminants such as low molecular weight hydrocarbons, alcohols and other oxygenates. A hot gaseous mixture containing CH4 and steam is used to strip pollutants from said condensate. The stripped contaminants, CH4 and steam are recovered separately from the remaining purified water as a gas stream. The gas stream containing the recovered CH4 can be used in syngas (CO/H ₂ ) production processes, with the subsequently produced syngas being used in a hydrocarbon synthesis process to produce heavy hydrocarbons.

All of the above methods described in the art are complex, expensive, and some are energy intensive. Accordingly, the following text details the innovations that make possible the direct use of catalyst reaction water without the need for purification and other pre-treatments.

Improved catalyst for direct fuel production.

The first aspect of the preferred embodiment is the implementation of an improved direct fuel catalyst 109b that has been designed to directly produce high quality liquid fuels and catalyst water of reaction free of unwanted carboxylic acids.

When the direct fuel catalyst described in US Pat. e.g., pH about 7.0), and when the oxygen concentration in the synthesis gas is less than about 500 to 1000 ppm, carboxylic acids are not formed or detected (<25 ppm) in the catalyst reaction water and fuel oil cuts.

Directly produced liquid fuels do not corrode, oxidize or decompose during storage and can be stored for several years without change. In addition, the catalyst reaction water can be directly recycled 112 to the synthesis gas generator 103 without any problems.

Improved redox catalyst for removing oxygen from synthesis gas.

In the presence of oxygen in the synthesis gas at concentrations greater than 500 ppm, some carboxylic acids may form. Therefore, an improved catalyst has been developed to remove oxygen present in synthesis gas at levels above about 500 ppm.

Catalytic steam reforming has been chosen as the preferred method for converting gas phase feedstocks to synthesis gas because the process does not use air or oxygen. Slow pyrolysis/steam reforming is the preferred method for producing synthesis gas from solid phase feedstocks because air is eliminated (Schuetzle et al., 2005). When appropriate measures are taken to exclude air from these processes, the synthesis gas will contain less than about 250 ppm of oxygen.

Direct recycling of catalyst reaction water.

Liquid fuels are separated using a three-phase separator 110 into tail gas 111 (Ci-C ₄ hydrocarbons, oxygenated hydrocarbons, CO2, and unreacted H2 and CO), catalyst reaction water 112 and liquid fuels 113 (mainly consisting of C ₅ -C ₂₄ hydrocarbons and oxygenated organic compounds).

Also get a small amount of wax (mainly consisting of C ₂₄ -C ₄₀ hydrocarbons). In one embodiment, less than 25% wax by weight will be obtained, preferably less than 5% wax by weight, with less than 2% wax being produced in a preferred embodiment.

In some embodiments, the tail gas 111 may be recycled to the thermochemical synthesis gas generator 103 where it may be converted to additional synthesis gas or used as heating oil.

Improved recycling of catalyst reaction water.

The second aspect of the preferred embodiment is direct recycling of the catalyst reaction water 112 to a synthesis gas process that requires steam to operate efficiently.

When using a synthesis gas generator requiring little or no steam, the catalyst reaction water can be used directly for secondary or tertiary oil recovery and for other uses such as generating steam for power generation or for water consumption in plants combined with this. equipment. Such

- 11 041315 innovation was made possible because the catalyst reaction water does not contain harmful carboxylic acids, but contains hydroxyalkanes (alcohols), which are excellent additives for secondary and tertiary oil recovery.

Local application of liquid fuel.

Liquid fuel 113 can be used directly and locally in off-highway engines used in diesel generators, tractors, compressors, water pumps, agricultural machinery, construction equipment, and the like.

Transportation of liquid fuel.

Liquid fuel 113 can be collected and transported by road and/or rail to a central location where it is distilled 115 to produce the high quality fuel products 116 shown in FIG. 3, for distribution to local fuel markets.

Possible distillation products of liquid fuel product 113 include: reformulated gasoline blending components (approximately C ₅ -C ₈ hydrocarbons and oxygenated organic compounds) 302; diesel fuel No. 1 (kerosene) (approximately C ₈ -C ₁₆ hydrocarbons and oxygenated organic compounds) 303; diesel fuel No. 2 304 (approximately C ₉ -C ₂₀ hydrocarbons and oxygenated organic compounds); diesel fuel No. 3 305 (approximately C ₁₆ -C ₂₅ hydrocarbons and oxygenated organic compounds); and a small wax fraction 306 (C ₂₄₊ hydrocarbons and oxygenated organic compounds). A small amount of gases (air and C ₂ -C ₅ ) 301 is obtained, as well as a small residue (mainly oxidized hydrocarbons) 307.

Alternative or additional methods can be used to further distill liquid hydrocarbons to separate valuable alpha-olefins, n-paraffins, hydroxyalkanes, or other valuable products from liquid fuels.

An alternative implementation includes the direct introduction of liquid fuels into the combined crude oil pipeline 117 at the wellhead of the oil, while these fuels are mixed with crude oil for transportation to the refinery and/or chemical processing plant. Since liquid fuels have a much lower density and viscosity than crude oil, they serve to improve the flow of oil through pipelines.

The methanol catalysts can be used in the improved catalytic reactor in conjunction with the catalytic reactor 108 to produce an intermediate methanol feed that can be transported to a refinery and/or chemical plant for further processing into fuels and/or chemical compounds.

In some embodiments, to prevent coking and other undesirable reactions in some synthesis gas generators 103, the ratio of water to carbon in the feedstock is adjusted in the range of 1.5-3.0/1.0 and preferably 2.0-3.0/1 ,0.

Although make-up water is required when starting the integrated process described in FIG. 1, catalytic reaction water will generally be sufficient to maintain an efficient catalytic steam reforming process without the need for make-up water.

Preparation of catalyst reaction water without carboxylic acids.

In table. 3 shows data for hydroxyalkanes and carboxylic acids in catalyst reaction water obtained from syngas catalysis, which was produced by steam reforming of natural gas, natural gas liquids and glycerol using an improved catalyst with a carrier having neutral surface properties. Although the hydroxyalkanes were found to be 12831 ppm, 16560 ppm and 18877 ppm, respectively, in the case of synthesis gas produced from these three raw materials, formic acid, acetic acid, propionic acid and malonic acid were not detected (detection limit of 25 ppm each ) in samples of catalyst reaction water.

Because hydroxyalkanes and carboxylic acids are partitioned between the catalyst reaction water and the fuels, the possible presence of carboxylic acids in liquid fuels can be readily determined using the ASTM D130 copper plate corrosion test. If there are carboxylic acids in the fuel, the surface of the copper plate will change color, while the designation 1a indicates the absence of corrosion and the content of carboxylic acids; while 4c is used when the fuel corrodes the copper plate to a dark brown/black color, indicating that the fuel contains unacceptable levels of carboxylic acids (ASTM International, 2012).

It was found that fuels obtained directly from the raw materials listed in table. 3 provided the result of test 1a, which confirmed that carboxylic acids were absent.

- 12 041315

Table 3. Concentration of Oxygenated Organic Compounds in Catalyst Reaction Water Produced from Syngas Produced from Various Gas-Phase Hydrocarbons Using a Direct Fuel Catalyst

oxygenated organic compound Resource of gas-phase hydrocarbons Natural gas Evaporated gas condensate liquids Evaporated glycerin Concentration (pp) in catalyst reaction water methanol 4470 4980 6177 ethanol 4890 5040 6529 1-Propanol 1970 1930 2209 1-Butanol 1980 2530 1888 1-Pentanol 1080 1380 1342 1-Hexanol 310 290 333 1-heptanol 111 60 67 1 - Octanol <25 <25 122 1-Nonanol <25 <25 <25 Formic acid <25 <25 <25 Acetic acid <25 <25 <25 propionic acid <25 <25 <25 Malonic acid <25 <25 <25 Total 12.831 16,560 18.877

Direct recycling and use of catalysed reaction water.

Since the catalyst reaction water shown in table. 3 does not contain harmful carboxylic acids, it can be directly recycled to the synthesis gas process and other uses without the need for pre-treatment and purification.

If syngas production processes do not require a lot of steam, such as a partial oxidation reformer (ROX), such catalyst reaction water can be used for secondary or tertiary recovery of additional oil from nearby oil wells or for other water use, as described in this document.

When oil is present in subterranean rocks such as sandstone, carbonate or shale, such oil can typically be developed by drilling a well into the reservoir, allowing existing pressure gradients to drive the oil up the wellbore. Such a process is known as primary mining. If and when the pressure gradients are not sufficient to produce the oil at the desired rate, an improved recovery method is usually implemented to recover more oil. This method is known as secondary mining.

Even after secondary recovery using water injection, large amounts of the original oil may remain in the reservoir. The proportion of non-recoverable hydrocarbon is usually the highest in the case of heavy oils, shale oil and complex formations. In some large oil fields, more than a billion barrels (0.16 billion cubic meters) of oil can remain after conventional water injection.

Then the focus is on tertiary methods of oil extraction. It is estimated that modern tertiary oil recovery methods can remove an additional 5 to 20% of the oil remaining in the reservoir. The development of efficient tertiary oil recovery strategies for more efficient oil recovery promises to have a significant economic impact. Modern methods of tertiary oil recovery are efficient, but expensive, since many oil producing areas have limited water supplies.

It was found that hydroxyalkanes (alcohols), consisting of from one to four carbon atoms, dissolved in water, are ideal in terms of tertiary oil recovery [US patent 7559372 (7/2009)]. However, adding mixed alcohols to local water sources for tertiary oil production is a very expensive procedure.

Because the catalyst reaction water derived from the improved catalyst described herein contains up to 2.0% by volume of C ₁ -C ₅ alcohols, it is ideal for direct use in tertiary oil recovery.

An improved process for producing liquid fuels from synthesis gas is described that utilizes direct recycling of catalyst reaction water to synthesis gas production processes without the need for water purification or other complicated and costly pre-treatment procedures. This improvement was made possible by the discovery and implementation of innovative technologies that eliminate the formation of harmful carboxylic acids, which are formed by catalysts that convert synthesis gas to hydrocarbon products when the synthesis gas contains oxygen. These technologies include: (1) the development of an improved, direct fuel oil catalyst made from carriers having a neutral pH surface and other key properties, and (2) an improved redox catalyst that efficiently removes oxygen contained in the synthesis fuel. gas. Since each of these innovations inhibits the formation of carboxylic acids during the catalytic conversion of synthesis gas, these acids are not found in catalyst reaction water and liquid fuels. As a result, water can be directly recycled and used without negative impacts on syngas production processes. This improved direct water recycling process eliminates the need for disposal, purification, or treatment of catalyst reaction water and significantly reduces fresh water requirements for synthesis gas liquid fuel plants. Since carboxylic acids are not formed during the catalytic conversion of the synthesis gas, these acids are also excluded from the directly produced fuel. As a result, the fuel does not cause corrosion and does not decompose during storage.

In FIG. 1 shows the main typical processes for the preferred embodiment of the invention.

Gas-phase, liquid-phase and solid-phase carbonaceous raw materials can be converted into synthesis gas using various thermochemical conversion methods. Many liquids are vaporizable and can be introduced as gas phase feedstocks. If the liquid phase raw material is difficult to evaporate, it can be introduced as an aerosol. If the raw material contains both volatile liquid and non-volatile solid phase materials, the procedures used to introduce the raw material become more complicated.

Gas-phase feedstocks may include natural gas, biogas, associated gas, flared gas, gaseous hydrocarbons (e.g., C ₂ -C ₄ ) a mixture of wide fraction light hydrocarbons or a mixture of natural gas liquids (NGL), individual components extracted from streams of natural gases such as ethane, propane, butane or other components, natural gas condensates (C ₅₊ ) or other similar gases or liquids (such as naphtha or condensate) that can readily vaporize to form gas.

Liquid phase feedstocks may include glycerol by-products from biodiesel production; residual hydrocarbon waste generated during oil refining; waste oil (lipids), waste oils and many other low-value liquid hydrocarbon resources.

Solid phase raw materials include plastics; agricultural waste; wood obtained from reforestation; plastics (non-chlorine) and other low-value solid carbonaceous resources.

Gas-phase raw materials.

With gas phase feedstocks, contaminants such as sulfur compounds can be removed 102 before the resource is introduced into the synthesis gas generator 103. The preferred syngas generator 103 uses a catalyst that efficiently converts gas phase hydrocarbons to syngas at operating temperatures below about 1700°F (about 930°C). Sufficient steam is supplied to the synthesis gas generator to maintain a steam to carbon weight ratio of about 2.0 to about 3.0. In such a process, the catalyst reaction water 112 is directly used to produce steam. In some cases, a small amount of make-up water may be required. This process is commonly referred to as catalytic steam reforming.

Exclusion of oxygen from synthesis gas.

Many synthesis gas generation processes use oxygen to produce synthesis gas, resulting in the presence of residual oxygen in the synthesis gas. In other cases, small amounts of air are loaded with the raw materials, some of which enters the synthesis gas. Additional sources of oxygen in the synthesis gas result from the introduction of air during feedstock feeds to the synthesis gas generator, and from the introduction of air during scrubbing processes used to remove particulates and tar from the synthesis gas.

Since the presence of oxygen in the syngas has a negative effect on the catalytic conversion of syngas in the fuel, such as the formation of harmful carboxylic acids and the oxidation of syngas conversion catalysts, it is important to reduce the oxygen content of the syngas to very low levels.

An improved redox catalyst 109a (FIG. 1) and 201 (FIG. 2) was developed to reduce oxygen levels to less than 1000 ppm.

This innovative redox catalyst consists of a copper lanthanide material supported on a support with a high specific surface area. This redox type catalyst is compatible for integrated use with Fischer-Tropsch catalysts, direct fuel catalysts (US Pat. The proposed improved redox catalyst was designed to operate at the same temperatures, pressures, and space velocities as the hydrocarbon catalysts 203 (FIG. 2).

Improved redox catalyst 201 contains from about 2 to 25 wt.h. copper and up to 0.5 wt.h. lanthanides (preferably lanthanum) per 100 parts by weight deposited on a substrate with a high specific surface area selected from the group consisting of silicon dioxide, alumina, carbon nanotubes and/or combinations thereof.

At typical catalyst operating temperatures of 400 to 450°F (about 204 to 232°C), the copper in the redox catalyst reacts rapidly with any molecular oxygen and hydrogen in the syngas to form water without attacking carbon monoxide. , as shown in Equation 6, which is a combination of Equations 4 and 5. Since the reaction of oxygen with a redox catalyst is exothermic, uncoated catalyst carrier 202 can be added after the redox catalyst 201 to dissipate this heat, thus protecting the catalysts to obtain hydrocarbons from possible thermal damage.

2Cu + O ₂ = 2CuO Equation 4

2CuO + 2H2 = Cu + H2O Equation 5

O2 + H2 = H2O Equation 6 (Equations 4 and 5 combined)

At a catalytic reactor operating temperature of about 400 to 450°F (about 204 to 232°C), copper oxides are reduced back to copper by the H ₂ contained in the synthesis gas to form water as shown in Equation 7. Thus, Cu/CuO functions as a redox catalyst, removing oxygen from the synthesis gas.

CuO ₂ + H ₂ \u003d Cu + HgO Equation 7

When the oxygen from the synthesis gas is sufficiently reduced, the content of carboxylic acids is minimized with some Fischer-Tropsch catalysts, which mainly form wax and catalyst water of reaction. In addition, the efficiency of hydrocarbon production is increased because these reduced catalysts do not undergo re-oxidation with oxygen.

The advantages of said redox catalyst 201 when used in conjunction with hydrocarbon production catalysts 203 are that: 1) similar supports can be used in the redox catalyst and hydrocarbon production catalysts; 2) similar preparation procedures can be used to prepare catalysts; 3) redox catalysts and catalysts for producing hydrocarbons are jointly loaded into catalytic reactors; 4) the procedures and conditions used for the activation (reduction) of redox catalysts and catalysts for the production of hydrocarbons using hydrogen are the same and; 5) when obtaining hydrocarbon products, these catalysts can operate effectively under the same conditions of temperature, pressure and space velocity.

Another aspect of the preferred embodiment is the direct recycling of the catalyst water of reaction 112. This innovation is made possible because the catalyst water of reaction is free of harmful carboxylic acids.

According to some embodiments of the invention, the catalyst reaction water 112 is directly recycled to the synthesis gas generator 103, in which the hydroxyalkanes in the catalyst reaction water are converted into additional synthesis gas. According to other embodiments of the present invention, the catalyst reaction water may be recycled to a steam boiler that, along with other water sources, generates steam as a feed to syngas processes.

When such an improved process, which allows for direct recycle of catalyst water of reaction, is used in conjunction with an improved fuel oil catalyst, the fuel oil primary product can be used directly or distilled 300 (FIG. 3) to produce the desired products 301-305 for distribution to different fuel markets.

Potential distillation products include: reformulated gasoline blending components or naphtha range products (approximately C ₅ -C ₈ hydrocarbons and oxygenated organics) 302; diesel fuel No. 1 (kerosene) 303; diesel fuel No. 2 304; diesel fuel No. 3 305; and a small fraction of 306 wax. A small amount of gases (C ₂ -C ₄ ) 301 is obtained, as well as a small residue. Alternative or additional processes can be used to further distill liquid hydrocarbons to produce valuable alpha-olefins, n-paraffins, solvents, lubricating oils, hydroxyalkanes and/or other valuable products.

When such an improved redox catalyst is used in conjunction with

- 15 041315 conventional Fischer-Tropsch catalysis (De Klerk, 2012), which mainly produces wax, said wax can be purified to liquid fuels and other hydrocarbon products using standard wax enrichment and/or purification processes.

In another embodiment, mixed alcohol catalysts may be used in the improved catalytic reactor 108, wherein said mixed alcohols may be transported to a refinery and/or chemical plant for further processing into fuels and/or chemical compounds.

In another embodiment, the methanol production catalysts can be used in the catalytic reactor 108 to produce an intermediate methanol feed that can be transported to a refinery and/or chemical plant for further processing into fuels and/or chemicals.

In some embodiments, to prevent coking and other undesirable reactions in the thermochemical synthesis gas generator 103, the ratio of water to carbon in the feedstock is controlled in the range of 1.0-3.0/1.0 and preferably 2.0-3.0/1 .0 to prevent coking (formation of carbon) and other undesirable reforming reactions.

Although make-up water is required when starting the integrated process described in FIG. 1, catalytic reaction water will generally be sufficient to maintain an efficient catalytic steam reforming process without the need for very large amounts of make-up water.

The above description of the embodiments of the present invention has been presented for purposes of illustration and description only. This description is not intended to be exhaustive or to limit the present invention to the forms described. Accordingly, many modifications and variations will be apparent to those skilled in the art. In addition, the above description is not intended to limit the present invention. The scope of the present invention is defined by the appended claims.

Several exemplary embodiments are provided showing the effect of directly recycled catalyst reaction water on synthesis gas composition.

Although the thermal steam reforming of methane should ideally provide a H2/CO ratio of 3.0/1.0 according to the reaction in Equation 8, additional H2 is formed from some of the methane according to Equation 9, resulting in the reaction stoichiometry given in Equation 10.

SND + HgO = CO + 3H2 Equation 8 (main) | 0.20CH4 + 0.3HgO = 0.1 CO2 + 0.1 CO + 0.7Hg Equation 9 (secondary)

1.2CHg + 1.3HgO = 1.1CO + ODSOg + 3.7Hg Equation 10 (Equations 8 and 9 combined)

As a result, the H2/CO ratio produced in a steam methane reformer is typically greater than 3.0 (Norbeck et al., 2008). As shown in Equation 3, the H2/CO ratio is 3.36.

According to equation 3, the required molar ratio of H2O to carbon should be at least 1.44, but preferably in the range of 2.0 to 3.0 to eliminate the possibility of formation of elemental carbon.

Since the catalyst water containing hydroxyalkanes is recycled to the syngas generator, the alcohols reduce the H2/CO ratio. As examples, Equations No. 11, 12, and 13 show the reaction products and the stoichiometry of the products obtained from the reformation of methanol, ethanol, and propanol.

CH3OH + H ₂ O \u003d CO + 2H ₂ + H ₂ O Equation 11

CH3CH2OH + 2H ₂ O \u003d 2CO + 4H ₂ + H ₂ O Equation 12

CH3CH2CH2OH + ZH ₂ O \u003d ZSO + 6H ₂ + H ₂ O Equation 13

In this case, reforming said hydroxyalkanes produces a synthesis gas with an H2/CO ratio of 2.0/1.0, which helps to control the H2/CO ratio in the synthesis gas within the required range of 1.8 to 2.4.

Quoted links.

References provided herein are summarized as US Patents; publication of US patent applications; foreign patents and articles in magazines and books.

- 16 041315

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Claims (17)

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Soc., Div. fuel chem. 2003, 823-24 (2003). CLAIM 1. A process for converting one or more carbonaceous raw materials into one or more hydrocarbons, comprising: a) converting one or more carbonaceous raw materials into synthesis gas; b) lowering the oxygen content of the synthesis gas and converting the synthesis gas to one or more hydrocarbons - 19,041,315 hydrogen chlorides and an aqueous fraction in a catalytic reactor containing a redox catalyst consisting of a copper lanthanide material deposited on a substrate with a high specific surface area selected from silicon dioxide, alumina, carbon nanotubes and/or combinations thereof, and a conversion catalyst, wherein the aqueous fraction contains less than 500 ppm of one or more carboxylic acids. 2. The method according to claim 1, characterized in that one or more carbon-containing raw materials are selected from the group consisting of gas-phase raw materials; liquid-phase raw materials; and solid phase raw materials. 3. The method according to claim 1, characterized in that one or more carboxylic acids are selected from the group consisting of methanoic acid; ethanoic acid; propanoic acid; butanoic acid; pentanoic acid; hexanoic acid; and octanoic acid. 4. The method according to claim 1, characterized in that the conversion catalyst is used to convert synthesis gas into one or more hydrocarbons and an aqueous fraction, while said conversion catalyst contains a carrier, while said carrier has a surface, the pH of which is from about 6 .0 to about 8.0. 5. The method according to claim 1, characterized in that one or more carbon-containing raw materials are converted into synthesis gas by generating synthesis gas, thereby obtaining synthesis gas with an oxygen content of more than 1000 ppm, while at least part The oxygen in the synthesis gas is reduced using a redox catalyst, thereby obtaining a synthesis gas with an oxygen content of less than 250 ppm. 6. The method according to claim 1, characterized in that the aqueous fraction contains less than 100 ppm of one or more carboxylic acids. 7. The method according to claim 1, characterized in that one or more carbon-containing raw materials are converted into synthesis gas by generating synthesis gas, while the specified synthesis gas is obtained with an oxygen content of more than 250 ppm, while the oxygen in the synthesis gas reduced using a redox catalyst, wherein the synthesis gas is converted into one or more liquid fuels and an aqueous fraction using a conversion catalyst, while the aqueous fraction contains less than 25 ppm of carboxylic acids. 8. The method according to claim 1, characterized in that the water fraction is recycled back to the synthesis gas production process, while the water is not treated to remove one or more carboxylic acids. 9. The method according to claim 1, characterized in that the water fraction is used for secondary or tertiary oil recovery, while said water is not treated to remove one or more carboxylic acids. 10. The method according to claim 1, characterized in that one or more hydrocarbons obtained from the conversion of synthesis gas contain less than 25% wax. 11. The method according to claim 2, characterized in that one or more carbon-containing raw materials are one or more gas-phase raw materials selected from the group consisting of natural gas; biogas; associated gas; flared gas; gaseous hydrocarbons; and individual components extracted from natural gas streams. 12. The method according to claim 2, characterized in that one or more carbonaceous raw materials are one or more liquid-phase raw materials selected from the group consisting of glycerin by-products resulting from the production of biodiesel; residual hydrocarbon waste generated during oil refining; waste fats; and used oils. 13. The method according to claim 2, characterized in that one or more carbonaceous raw materials are one or more solid phase raw materials selected from the group consisting of plastics; agricultural waste; and wood obtained from forest reclamation. 14. The method according to claim 4, characterized in that the conversion catalyst carrier is alumina. 15. The method according to claim 4, characterized in that one or more carbon-containing raw materials are converted into synthesis gas by generating synthesis gas, thereby obtaining synthesis gas with an oxygen content of more than 1000 ppm, while at least part The oxygen in the synthesis gas is reduced using a redox catalyst, thereby obtaining a synthesis gas with an oxygen content of less than 250 ppm. 16. The method of claim 5, wherein the redox catalyst comprises a copper lanthanide material containing more than two percent by weight of copper and less than one percent by weight of lanthanide, wherein the redox catalyst is applied to a substrate with a high specific a surface selected from the group consisting of alumina, silicon dioxide, carbon and mixtures thereof. 17. The method of claim 15, wherein the redox catalyst is operated under the same temperature, pressure and space velocity conditions as the conversion catalyst. -